Pyrimidine derivatives and herbicides containing them

ABSTRACT

Pyrimidine derivatives having excellent herbicidal activities for crop plants and selectivity between crop plants and weeds, are presented. Pyrimidine derivatives represented by the following formula (I):                    
     wherein R 1  is a hydrogen atom, an alkyl group, a haloalkyl group or the like; R 2  is an alkyl group, a phenyl group which may be substituted, or the like; R 3  is a hydrogen atom, an alkyl group, an alkynyl group or the like; R 7  is a hydrogen atom, a halogen atom, an alkyl group or the like; R 8  is a hydrogen atom, an alkyl group or the like, W is a —C(═Q) Z— group or a —SO 2 — group; Q is O or S; Z is O, S, a —C(R 4 )R 5 —, a —NR 6  group or the like; each of R 4  and R 5  is a hydrogen atom, an alkyl group, an alkoxy group or the like; R 6  is a hydrogen atom or an alkyl group; and Ar is a phenyl group which may be substituted, a pyridyl group which may be substituted, or the like, and herbicides containing such pyrimidine derivatives as active ingredients.

TECHNICAL FIELD

The present invention relates to novel pyrimidine derivatives andherbicides containing them as active ingredients.

BACKGROUND ART

Pyrimidine derivatives are known, for example, by the specification ofinternational application WO95/12582, the specification of internationalapplication WO96/22980 and the specification of internationalapplication WO97/12877. However, the pyrimidine derivatives of thepresent invention have not been known.

A herbicide to be used for crop plants is desired to be a chemical whichexhibits a sufficient herbicidal effect at a low dose and yet providesselectivity between crop plants and weeds, when applied to an uplandfield or to a paddy field. Accordingly, it is an object of the presentinvention to provide a compound which has an excellent herbicidalactivity and selectivity between crop plants and weeds.

DISCLOSURE OF THE INVENTION

Under these circumstances, the present inventors have synthesizedvarious substituted pyrimidine derivatives and have studied theirphysiological activities. As a result, it has been found that novelsubstituted pyrimidine derivatives as the compounds of the presentinvention have excellent herbicidal activities and selectivity betweencrop plants and weeds, and the present invention has been accomplished.Namely, the present invention provides a pyrimidine derivativerepresented by the formula (I)

wherein R¹ is a hydrogen atom (except for a case where R²=hydrogen atom,and W═SO₂), a halogen atom, a C₁-C₆ alkyl group, a C₁-C₆ alkylcarbonylC₁-C₆ alkyl group, a hydroxyl group, a C₂-C₆ alkenyl group, a C₂-C₆alkynyl group, a C₃-C₆ cycloalkyl group (this group may be substitutedby a halogen atom, a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group or a C₁-C₄haloalkyl group), a C₁-C₄ haloalkyl group, a C₁-C₆ alkoxy group, a C₁-C₄haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₂-C₆ alkynyloxy group, aC₃-C₆ cycloalkyloxy group, a phenyl group (this group may be substitutedby a halogen atom, a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group, a C₁-C₄haloalkyl group, a C₁-C₄ haloalkoxy group, a cyano group, a cyano C₁-C₆alkyl group, a nitro group, a C₁-C₆ alkylthio group, a C₁-C₆alkylsulfinyl group or a C₁-C₆ alkylsulfonyl group), a C₁-C₆ alkylthiogroup (except for a case where R²=phenyl group, and W═SO₂), a C₂-C₆alkenylthio group, a C₂-C₆ alkynylthio group, a C₃-C₆ cycloalkylthiogroup, a C₁-C₆ alkylsulfinyl group, a C₂-C₆ alkenylsulfinyl group, aC₂-C₆ alkynylsulfinyl group, a C₃-C₆ cycloalkylsulfinyl group, a C₁-C₆alkylsulfonyl group, a C₂-C₆ alkenylsulfonyl group, a C₂-C₆alkynylsulfonyl group, a C₃-C₆ cycloalkylsulfonyl group, a C₁-C₆hydroxyalkyl group, a C₂-C₇ acyl group, a C₁-C₆ alkoxy C₁-C₆ alkylgroup, a cyano group, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆alkoxycarbonyl C₁-C₆ alkyl group, a C₁-C₆ alkoxycarbonyl C₂-C₆ alkenylgroup, a carboxyl group, a carboxyl C₁-C₆ alkyl group, a di C₁-C₆ alkoxyC₁-C₆ alkyl group, a C₁-C₆ alkoxyimino C₁-C₆ alkyl group, a hydroxyiminoC₁-C₆ alkyl group, a dioxolanyl group (this group may be substituted bya C₁-C₆ alkyl group), an aldehyde group, an oxiranyl group, a NR⁹R¹⁰group or a CONR⁹R¹⁰ group, R⁹ is a hydrogen atom, a C₁-C₆ alkyl group, aC₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₄ haloalkyl group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a C₁-C₆ alkylthio C₁-C₆ alkyl group, aC₃-C₆ cycloalkyl group, a C₂-C₇ acyl group or a C₁-C₆ alkylsulfonylgroup, R¹⁰ is a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆alkynyl group, a C₁-C₄ haloalkyl group, a C₁-C₆ alkoxy C₁-C₆ alkylgroup, a C₁-C₆ alkylthio C₁-C₆ alkyl group, a C₃-C₆ cycloalkyl group, aC₂-C₇ acyl group, a C₁-C₆ alkylsulfonyl group, a C₁-C₆ alkoxycarbonylgroup or a benzyloxycarbonyl group, here R⁹ and R¹⁰ may, together withthe carbon atom to which they are bonded, form a 5- to 7-memberedsaturated ring, R² is a hydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkylthio group, a C₁-C₄haloalkyl group, a C₁-C₆ alkoxy group, a C₁-C₆ alkoxy C₁-C₆ alkyl group,a C₁-C₆ alkylthio C₁-C₆ alkyl group, a C₃-C₆ cycloalkyl group (thisgroup may be substituted by a halogen atom, a C₁-C₆ alkyl group, a C₁-C₆alkoxy group or a C₁-C₄ haloalkyl group), a C₂-C₇ acyl group, a cyanogroup, a di C₁-C₆ alkoxy C₁-C₆ alkyl group, a C₁-C₆ alkoxyimino C₁-C₆alkyl group, a hydroxyimino C₁-C₆ alkyl group, a dioxolanyl group (thisgroup may be substituted by a C₁-C₆ alkyl group), a cyano C₁-C₆ alkylgroup, a C₁-C₆ hydroxyalkyl group, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆alkoxycarbonyl C₁-C₆ alkyl group, a CR¹¹R¹²NR⁹R¹⁰ group, a CONR⁹R¹⁰group, a CR¹¹R¹²CONR⁹R¹⁰ group or a group represented by any one of theformulae R²-1 to R²-13:

(wherein X is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group, aC₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkoxy group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a NR⁹R¹⁰ group, a CONR⁹R¹⁰ group, aC₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₃-C₆ cycloalkyloxygroup, a s C₂-C₇ acyl group, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆alkylthio group, a C₁-C₆ alkylsulfinyl group, a C₁-C₆ alkylsufonylgroup, a cyano group, a nitro group or a C₁-C₄ haloalkyl group, n is aninteger of from 1 to 3, when n is an integer of 2 or 3, the plurality ofX may be the same or different, and two adjacent lower alkoxy groups maybe bonded to each other to form a C₁-C₃ alkylenedioxy group), each ofR¹¹ and R¹² is a hydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆ alkenylgroup, a C₂-C₆ alkynyl group or a C₁-C₆ alkoxy group, R³ is a hydrogenatom, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group,a C₁-C₆ alkoxy group, a di C₁-C₆ alkylamino group, a C₃-C₆ cycloalkylgroup, a C₁-C₆ alkoxy C₁-C₆ alkyl group, a cyano C₁-C₆ alkyl group, aC₃-C₆ cycloalkyl C₁-C₆ alkyl group, an oxiranyl C₁-C₆ alkyl group or aC₁-C₆ alkoxycarbonyl C₁-C₆ alkyl group, W is a —C(═Q)Z— group or a —SO₂—group, Q is an oxygen atom or a sulfur atom, Z is an oxygen atom, asulfur atom, a —NR⁶— group, a —CH₂CH₂— group, a —CH═CH— group, a—C(R⁴)R⁵— group, a —C(R⁴)R⁵—Q— group, a —Q—C(R⁴)R⁵— group, a —C(═Q)—group, a —NR⁶NR^(6a)— group or a —NR⁶C(R⁴)R⁵— group, each of R⁴ and R⁵is a hydrogen atom, a C₁-C₆ alkyl group, a halogen atom, a C₁-C₆ alkoxygroup or a C₁-C₆ alkylthio group, each of R⁶ and R^(6a) is a hydrogenatom, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group or a C₂-C₆ alkynylgroup, here R³ and R⁶ may, together with the carbon atom to which theyare bonded, form a 5- to 7-membered cyclic urea, Ar is a grouprepresented by any one of the formulae Ar-1 to Ar-17:

(wherein X′ is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group, aC₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkoxy group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a NR⁹R¹⁰ group, a CONR⁹R¹⁰ group, aC₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₃-C₆ cycloalkyloxygroup, a C₂-C₇ acyl group, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆alkylthio group, a C₁-C₆ alkylsulfinyl group, a C₁-C₆ alkylsufonylgroup, a cyano group, a nitro group or a C₁-C₄ haloalkyl group, n′ is aninteger of from 1 to 3, m is an integer of from 0 to 3, when n′ is aninteger of 2 or 3, the plurality of X′ may be the same or different, andtwo adjacent lower alkoxy groups may be bonded to each other to form aC₁-C₃ alkylenedioxy group), R⁷ is a hydrogen atom, a halogen atom, aC₁-C₆ alkyl group, a C₁-C₆ alkoxy group, a C₁-C₆ alkylthio group, aC₁-C₄ haloalkyl group or a C₃-C₆ cycloalkyl group, and R⁸ is a hydrogenatom, a C₁-C₆ alkyl group, a C₁-C₆ alkylthio group, a C₁-C₄ haloalkylgroup or a C₃-C₆ cycloalkyl group; and a herbicide containing it as anactive ingredient.

Now, definitions of terms used in this specification will be shownbelow.

The halogen atom represents a fluorine atom, a chlorine atom, a bromineatom or an iodine atom.

The C₁-C₆ alkyl group means a straight chain or branched chain alkylgroup having a carbon number of from 1 to 6, unless otherwise specified,and it may, for example, be a methyl group, an ethyl group, a n-propylgroup, an isopropyl group, a n-butyl group, an isobutyl group, asec-butyl group or a tert-butyl group.

The C₃-C₆ cycloalkyl group represents a cycloalkyl group having a carbonnumber of from 3 to 6, and it may, for example, be a cyclopropyl group,a cyclopentyl group or a cyclohexyl group.

The C₂-C₆ alkenyl group represents a straight chain or branched chainalkenyl group having a carbon number of from 2 to 6, and it may, forexample, be an ethenyl group or a 2-propenyl group.

The C₂-C₆ alkynyl group represents a straight chain or branched chainalkynyl group having a carbon number of from 2 to 6, and it may, forexample, be an ethynyl group or a 2-propynyl group.

The C₁-C₄ haloalkyl group represents a straight chain or branched chainalkyl group having a carbon number of from 1 to 4, which is substitutedby from 1 to 9 same or different halogen atoms, unless otherwisespecified, and it may, for example, be a chloromethyl group, atrifluoromethyl group or a tetrafluoroethyl group.

The C₁-C₆ alkoxy group represents an (alkyl)-O-group wherein the alkylmoiety has the above meaning, and it may, for example, be a methoxygroup, an ethoxy group or a propoxy group.

The C₂-C₆ alkenyloxy group represents an (alkenyl)-O-group wherein thealkenyl moiety has the above meaning, and it may, for example, be anethenyloxy group or a 2-propenyloxy group.

The C₂-C₆ alkynyloxy group represents an (alkynyl)-O-group wherein thealkynyl moiety has the above meaning, and it may, for example, be anethynyloxy group or a 2-propynyloxy group.

The C₃-C₆ cycloalkyloxy group represents a (cycloalkyl)-O-group whereinthe cycloalkyl moiety has the above meaning, and it may, for example, bea cyclopropyloxy group, a cyclopentyloxy group or a cyclohexyloxy group.

The C₁-C₆ alkoxy C₁-C₆ alkyl group represents an(alkyl)-O-(alkylene)-group, wherein the alkyl moiety has the abovemeaning, and it may, for example, be a methoxymethyl group or anethoxymethyl group.

The C₃-C₆ cycloalkyl C₁-C₆ alkyl group represents a (cycloalkyl)-(C₁-C₆alkylene) group wherein the cycloalkyl moiety has the above meaning, andit may, for example, be a cyclopropylmethyl group, a cyclopentylmethylgroup, a cyclohexylmethyl group or a cyclohexylethyl group.

The C₁-C₄ haloalkoxy group represents a (haloalkyl)-O-group wherein thehaloalkyl moiety has the above meaning, and it may, for example, be atrifluoromethoxy group or a 2,2,2-trifluoroethoxy group.

The C₁-C₆ alkylthio group, the C₁-C₆ alkylsulfinyl group and the C₁-C₆alkylsulfonyl group, represent an (alkyl)-S-group, an (alkyl)-SO-groupand an (alkyl)-SO₂-group, wherein the alkyl moiety has the abovemeaning, and they may, for example, be a methylthio group, an ethylthiogroup, a methylsultinyl group, an ethylsulfinyl group, a methylsulfonylgroup or an ethylsulfonyl group.

The C₂-C₆ alkenylthio group, the C₂-C₆ alkenylsulfinyl group and theC₂-C₆ alkenylsulfonyl group, represent an (alkenyl)-S-group, an(alkenyl)-SO-group and an (alkenyl)-SO₂-group, wherein the alkenylmoiety has the above meaning, and they may, for example, be apropenylthio group, a butenylthio group, a propenylsulfinyl group, abutenylsulfinyl group, a propenylsulfonyl group or a butenylsulfonylgroup.

The C₂-C₆ alkynylthio group, the C₂-C₆ alkynylsulfinyl group and theC₂-C₆ alkynylsulfonyl group, represent an (alkynyl)-S-group, an(alkynyl)-SO-group and an (alkynyl)-SO₂-group, wherein the alkynylmoiety has the above meaning, and they may, for example, be anethynylthio group, a 2-propynylthio group, an ethynylsulfinyl group, a2-propynylsulfinyl group, an ethynylsulfonyl group or a2-propynylsulfonyl group.

The C₃-C₆ cycloalkylthio group, the C₃-C₆ cycloalkylsulfinyl group andthe C₃-C₆ cycloalkylsulfonyl group, represent a (cycloalkyl)-S-group, a(cycloalkyl)-SO-group, and a (cycloalkyl)-SO₂-group, wherein thecycloalkyl moiety has the above meaning, and they may, for example, be acyclopropylthio group, a cyclobutylthio group, a cyclopentylthio group,a cyclohexylthio group, a cyclopropylsulfinyl group, acyclobutylsulfinyl group, a cyclopentylsulfinyl group, acyclohexylsulfinyl group, a cyclopropylsulfonyl group, acyclobutylsulfonyl group, a cyclopentylsulfonyl group or acyclohexylsulfonyl group.

The C₁-C₆ alkylthio C₁-C₆ alkyl group represents an (alkyl)-S-(alkylene)group wherein the alkyl moiety has the above meaning, and it may, forexample, be a methylthiomethyl group, an ethylthiomethyl group, apropylthiomethyl group or a methylthioethyl group.

The C₂-C₇ acyl group represents a C₁-C₆ alkylcarbonyl group, a C₂-C₆alkenylcarbonyl group, a C₂-C₆ alkynylcarbonyl group, a C₃-C₆cycloalkylcarbonyl group or a benzoyl group, and it may, for example, bean acetyl group, a propionyl group, a n-butyryl group, an isobutyrylgroup, a cyclopropylcarbonyl group or a benzoyl group.

The C₁-C₆ alkylcarbonyl C₁-C₆ alkyl group may, for example, be amethylcarbonylmethyl group, an ethylcarbonylmethyl group or apropylcarbonylmethyl group.

The diC₁-C₆ alkoxy C₁-C₆ alkyl group may, for example, be adimethoxymethyl group or a diethoxymethyl group.

The C₁-C₆ alkoxyimino C₁-C₆ alkyl group may, for example, be amethoxyiminomethyl group or an ethoxyiminomethyl group.

The hydroxyimino C₁-C₆ alkyl group may, for example, be ahydroxyiminomethyl group or a hydroxyiminoethyl group.

The cyano C₁-C₆ alkyl group may, for example, be a cyanomethyl group ora cyanoethyl group.

The C₁-C₆ hydroxyalkyl group may, for example, be a hydroxymethyl groupor a hydroxyethyl group.

The C₁-C₆ alkoxycarbonyl group may, for example, be a methoxycarbonylgroup or an ethoxycarbonyl group.

The C₁-C₆ alkoxycarbonyl C₁-C₆ alkyl group may, for example, be amethoxycarbonyl methyl group or an ethoxycarbonyl methyl group.

The carboxyl C₁-C₆ alkyl group may, for example, be a carboxymethylgroup or a carboxyethyl group.

The diC₁-C₆ alkoxy C₁-C₆ alkyl group may, for example, be adiethoxymethyl group or a 2-dimethoxyethyl group.

The diC₁-C₆ alkylamino group is a dialkylamino group wherein thealkylalkyl moiety has the above meaning, and it may, for example, be adimethylamino group or a diethylamino group.

BEST MODE FOR CARRYING OUT THE INVENTION

Now, typical specific examples of the compound of the present inventionrepresented by the formula (I) will be exemplified in Tables 1 to 39.However, the compound of the present invention is not limited to suchcompounds. The compound numbers will be referred to in the subsequentdescription. Further, in a case where the compound of the presentinvention or the disclosed compound has at least one asymmetric carbon,its all steric isomers are included in the compound of the presentinvention.

In the tables in this specification, S-isomer and R-isomer representS-isomer and R-isomer of optical isomers, respectively, and in a casewhere there is no specific representation even when the compound has anasymmetric carbon, such represents a racemate. Further, in the tables,A-isomer and B-isomer represent diastereomers such that when resolved bysilica gel column chromatography, one eluting first is designated asA-isomer, and one eluting later is designated as B-isomer. In a casewhere there is no representation even if diastereomers exist, suchrepresents a mixture of diastereomers.

The following representations in the tables in this specificationrepresent the respective corresponding groups as shown below.

Me: methyl group Et: ethyl group Pr: n-propyl group Pr-i: isopropylgroup Pr-c: cyclopropyl group Bu: n-butyl group Bu-i: isobutyl groupBu-s: sec-butyl group Bu-t: tert-butyl group Bu-c: cyclobutyl group Pen:n-pentyl group Pen-i: isopentyl group Pen-c: cyclopentyl group Hex-c:cyclohexyl group

 

TABLE 1

m. p. (° C.) or refractive Compound index No. R¹ R² R³ Z Xn QDiastereomer (n_(D) ²⁰) 1-1  CClF₂ Pr-c H CH₂ H O 124-127 1-2  CClF₂Pr-c H CH₂ 4-OMe O 116-119 1-3  CClF₂ Pr-c H CH₂ 4-Cl O 125-128 1-4 CClF₂ Pr-c H CH₂ 4-CF₃ O 111-114 1-5  CF₃ Pr-i H CH₂ H O 144-146 1-6 CF₃ Pr-i H CH₂ 4-OMe O 114-117 1-7  CF₃ Pr-i H CH(Me) H O 1.5163 1-8 CF₃ Pr-i Me CH₂ H O 106-109 1-9  CF₃ Pr-i Me CH₂ 4-OMe O 1.5289 1-10 CF₃Pr-i Me S H O 131-133 1-11 CF₃ Pr-i Me S 4-OMe O 156-159 1-12 CF₃ Pr-iMe CH₂ 4-F O 109-110 1-13 CF₃ Pr-i Me CH₂ 4-OEt O 1.5151 1-14 CF₃ Pr-iMe S 4-Cl O 1-15 CClF₂ Pr-i Me CH₂ H O 109-112 1-16 CClF₂ Pr-i Me CH₂4-OMe O Not Measurable 1-17 CClF₂ Pr-i Me S H O 127-130 1-18 CClF₂ Pr-iMe S 4-OMe O 136-139 1-19 CClF₂ Pr-i Me O H O 115-118 1-20 CF₃ Pr-i MeCH₂ 2-Cl O 178-181 1-21 CF₃ Pr-i Me CH₂ 3-Cl O 122-125 1-22 CF₃ Pr-i MeCH₂ 4-Cl O  99-101 1-23 CF₃ Pr-i Me CH₂ 4-Me O  76-79 1-24 CF₃ Pr-i MoCH₂ 4-CF₃ O 105-108 1-25 CClF₂ Pr-i Me CH₂ 4-F O 126-129 1-26 CF₃ Pr-iEt CH₂ H O  87-90 1-27 CF₃ Pr-i Et CH₂ 4-F O 130-132 1-25 CF₃ Pr-i Me NHH O 149-150 1-29 CF₃ Pr-i Me NH 4-Cl O

 

TABLE 2 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1-30 CF₃ Me Me CH₂ H O 1.5258 1-31 CF₃ Me MeCH₂ 4-F O 1.5202 1-32 CF₃ Et Me CH₂ H O 40-41 1-33 CF₃ Et Me CH₂ 4-F O72-73 1-34 CF₃ Pr-c Me CH₂ H O Not Measurable 1-35 CF₃ Pr-c Me CH₂ 4-F O97-99 1-36 CF₃ Ph Me CH₂ 4-F O 93-94 1-37 CClF₂ Pr-i Me NH 4-Me O135-137 1-38 CClF₂ Pr-i Me NH H O 146-147 1-39 CF₃ Pr-i Me CH₂ 3-CF₃ O119-120 1-40 CF₃ Pr-i Me CH₂ 2,5-F₂ O 145-146 1-41 CF₃ Pr-i Me CH₂ 4-BrO 93-95 1-42 CF₃ Pr-i Me CH₂ 4-I O 102-104 1-43 CF₃ Pr-i Me CH₂ 4-Bu-t O101-102 1-44 CF₃ Pr-i Me CH₂ 4-SMe O 69-71 1-45 CF₃ Pr-i Me CH₂ 3,4-Cl₂O 145-146 1-46 CF₃ Pr-i Me CH₂ 2-F,4-Cl O 115-116 1-47 CF₃ Pr-i Me CH₂3-OMe,4-Cl O 129-131 1-48 CF₃ Pr-i Et CH₂ 4-Cl O 120-123 1-49 CF₃ Pr-iPr CH₂ 4-Cl O 140-141 1-50 CF₃ Pr-i Me CH₂ 2-Me O 154-155 1-51 CF₃ Pr-iMe CH₂ 3-Me O 93-94 1-52 CF₃ Pr-i Me CH₂ 4-NO₃ O 146-149 1-53 CF₃ Bu-tMe CH₂ 4-F O 91-92 1-54 CF₃ Bu-t Me CH₂ 4-Cl O 111-112 1-55 CF₃ Bu-t MeCH₂ 4-Me O 84-87 1-56 CH₃ Pr-i Me CH₂ 4-Cl O 118-119 1-57 CF₃ Bu-s MeCH₂ H O 70-71 1-58 CF₃ Bu-s Me CH₂ 4-F O 84-85 1-59 CF₃ Bu-s Me CH₂ 4-ClO 73-75 1-60 CF₃ Bu-s Me CH₂ 4-Me O 61-64 1-61 CF₃ Pr-i Et CH₂ 4-Me O92-94 1-62 CF₃ Pr-i Pr CH₂ 4-Me O 83-86 1-63 CF₃ Pr-i Pr CH₂ H O 146-1471-64 CF₃ Pr-i Me CH₂O H O 117-119 1-65 CF₃ Pr-i Me CH₂O 4-Cl O 141-142

 

TABLE 3 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1-66 CF₃ Pr-i Me CH₂ 3-F O 120-123 1-67 CF₃Pr-i Me CH₂ 4-Et O 56-58 1-68 CF₃ Pr-i Me CH₂ 4-Pr-i O 86-87 1-69 Pr-iPr-i Me CH₂S H O 1-70 CF₈ Pr-i Me CH₂ 3-Br O 120-121 1-71 CF₃ Pr-i MeCH(Me) 4-Cl O 1.5232 1-72 CF₃ Pr-i Me CH₂ 3,4-(Me)₂ O 83-85 1-73 Pr-iPr-i Me CH₂S 4-Cl O 1-74 CF₃ Pr-i Me CH₂ 3-NO₂ O 118-121 1-75 CF₃ Pr-iMe CH₂ 4-CN O 141-142 1-76 CF₃ Pr-i Me CH₂ 4-CH₂OMe O 58-60 1-77 CF₃Pr-i Me CH₂CH₂ H O 79-82 1-78 Pr-c Pr-i Me CH₂ 4-Cl O 110-113 1-79 Pr-iMe Me CH₂ H O 69-70 1-80 CF₃ Pr-i Pr-c CH₂ H O 83-86 1-81 CF₃ Pr-i Pr-cCH₂ 4-Cl O 1.5297 1-82 CF₃ Pr-i Pr-c CH₂ 4-Me O 1.5218 1-83 CF₃ Pr-iPr-c CH₂ 4-F O 81-84 1-84 CF₃ Pr-i Me CH₂ 4-C≡CMe O 128-132 1-85 CF₃Pr-i Me CH═CH H O 1.5375 1-86 CF₃ Pr-i Me CH═CH 4-Cl O 1.5565 1-87 MePr-i Me CH₂ H O 80-83 1-88 Me Pr-i Me CH₂ 4-F O 102-104 1-89 Me Pr-i MeCH₂ 4-Me O 106-107 1-90 H Pr-i Me CH₂ 4-Cl O 1.5503 1-91 CClF₂ Pr-c MeCH₂ H O 111-113 1-92 CClF₂ Pr-c Me CH₂ 4-F O 91-92 1-93 CClF₂ Pr-c MeCH₂ 4-Me O 87-88 1-94 CClF₂ Pr-c Me CH₂ 4-Cl O 112-114 1-95 CF₃ Pr-i MeCH₂ 4-OCF₃ O 80-81 1-96 CF₃ Pr-i Me CH₂ 4-OCHF₂ O 54-57 1-97 CF₃ Pr-i MeCH₂ 4-OPr-i O 74-75 1-98 CF₃ Pr-i Et CH₂ 4-CN O 139-142 1-99 CF₃ Pr-i PrCH₂ 4-CN O 162-163 1-100 CF₃ Pr-i Me CH₂ 2-F O 163-164 1-101 Pr-c Pr-iMe CH₂ 4-F O 111-112

 

TABLE 4 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1-102 Pr-c Pr-i Me CH₂ 4-Me O 81-83 1-103 CF₃Pr-i Pr-i CH₂ H O 1.5131 1-104 CF₃ Pr-i Me CH₂ 4-SO₂Me O 137-139 1-105CF₃ Pr-i CH₂OMe CH₂ 4-Cl O 142-145 1-106 CF₃ Pr-i CH₂OMe CH₂ 4-Me O104-106 1-107 CF₃ Pr-i CH₂OEt CH₂ 4-Me O 91-94 1-108 CF₃ Pr-i Me O 4-F O1-109 CF₃ Pr-i Me O 4-Me O 1-110 CF₃ Pr-i Me O 4-Cl O 1-111 CF₃ Pr MeCH₂ H O 54-55 1-112 CF₃ Pr Me CH₂ 4-F O 67-70 1-113 CF₃ Pr Me CH₂ 4-Me O63-64 1-114 CF₃ Pr Me CH₂ 4-Cl O 91-92 1-115 CF₃ Pr-i Me CH(Me)O H O127-130 1-116 CF₃ Pr-i Me CH(Me)O 4-Cl O 104-105 1-117 CF₃ Pr-i MeCH(Me)O 4-Me O 1-118 CF₃ Pr-i Me OCH₂ H O 1.5028 1-119 CF₃ Pr-i Me CH₂S-OMe,4-Me O 1.5109 1-120 CF₃ Pr-i Me CH₂ 3-Me,4-Cl O 92-94 1-121 CF₃Pr-i Me CH₂ 3-Cl,4-Me O 121-122 1-122 CF₃ Pr-i Me CH₂ 3,4-F₂ O 135-1361-123 CF₃ Pr-i Me CH₂ 2,6-F₂ O 176-177 1-124 CF₃ Pr-i Me CH₂ 2,4-Cl₂ O147-149 1-125 CF₃ Pr-i Me CH₂O 2-F O 157-158 1-126 CF₃ Pr-i Me CH₂O 3-FO 127-128 1-127 CF₃ Pr-i Me CH₂O 4-F O 119-121 1-128 Pr-i Pr-i Me CH₂ HO 118-119 1-129 Pr-i Pr-i Me CH₂ 4-F O 125-126 1-130 Pr-i Pr-i Me CH₂4-Cl O 123-126 1-131 Pr-i Pr-i Me CH₂ 4-Me O 110-113 1-132 CF₃ Pr-i MeCH₂O 2-Cl O 162-163 1-133 CF₃ Pr-i Me CH₂O 3-Cl O 122-124 1-134 CF₃ Pr-iMe CH₂O 2-Me O 136-138 1-135 CF₃ Pr-i Me CH₂O 3-Me O 117-119 1-136 CF₃Pr-i Me CH₂O 4-Me O 140-141 1-137 CF₃ Pen-c Me CH₂ H O 72-74

 

TABLE 5 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1-138 CF₃ Pen-c Me CH₂ 4-F O 97-99 1-139 CF₃Pen-c Me CH₂ 4-Cl O 55-57 1-140 CF₃ Pen-c Me CH₂ 4-Br O 69-71 1-141 CF₃Pen-c Me CH₂ 4-Me O 76-78 1-142 CF₃ Pr-i Me CH₂ H S 93-94 1-143 CF₃ Pr-iMe CH₂ 4-F S 103-104 1-144 CF₃ Pr-i Me CH₂ 4-Cl S 92-93 1-145 CF₃ Pr-iMe CH₂ 4-Me S 1.5541 1-146 CF₃ Pr-i Me CH₂ 3,4-(-OCH₂O-) O 82-85 1-147CF₃ Pr-i Me CH₂ 2,4-F₂ O 137-139 1-148 CF₃ Pr-i Me CH₂ 2,3-F₂ O 183-1841-149 CF₃ Pr-i Me CH₂ 2,3,4-F₃ O 1-150 SMe Pr-i Me CH₂ H O 88-89 1-151SMe Pr-i Me CH₂ 4-Cl O 125-127 1-152 SMe Pr-i Me CH₂ 4-F O 121-124 1-153SMe Pr-i Me CH₂ 4-Me O 78-79 1-154 CF₃ Pr-i Me CH(SMe) 4-Cl O 148-1491-155 CF₃ Pr-i Me CH(OMe) 4-Cl O 107-108 1-156 CF₃ Pen-c Me CH₂ 2-F O111-112 1-157 CF₃ Pr-i Me CH₂ 4-N(Me)₂ O 109-111 1-158 CF₃ Ph(4-F) MeCH₂ 3-F O 85-86 1-159 CH₃ Bu-t Me CH₂ H O 93-95 1-160 CH₃ Bu-t Me CH₂4-F O 96-98 1-161 CH₃ Bu-t Me CH₂ 4-Cl O 107-109 1-162 CH₃ Bu-t Me CH₂4-Me O 84-86 1-163 CHF₂ Pr-i Me CH₂ H O 62-65 1-164 CHF₂ Pr-i Me CH₂ 4-FO 82-84 1-165 CHF₂ Pr-i Me CH₂ 4-Cl O 85-87 1-166 CHF₂ Pr-i Me CH₂ 4-MeO 83-84 1-167 CF₃ Pr-i Me CH₂ 3,5-F₂ O 156-157 1-168 CHF₂ Pr-i Et CH₂ HO 85-86 1-169 CHF₂ Pr-i Et CH₂ 4-F O 100-103 1-170 CHF₂ Pr-i Et CH₂ 4-ClO 114-117 1-171 CHF₂ Pr-i Et CH₂ 4-Me O 91-92 1-172 CF₃ Pr-i CH₂C≡CH CH₂4-F O 124-128

 

TABLE 6 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1-173 CF₃ Pr-i Et CH₂ 3-F O 119-121 1-174 CF₃Pr-i Et CH₂ 4-CF₃ O 100-101 1-175 CF₃ Pr-i Me C(Me)₂ 4-Me O 108-1101-176 CF₃ Pr-i Me O H O 80-81 1-177 CF₃ Pr-i Me O 4-F O 110-112 1-178CF₃ Pr-i Me O 4-Cl O 112-115 1-179 CF₃ Pr-i Me O 4-Me O 94-97 1-180 CF₃Pr-i Me CH₂ 3-F,4-Cl O 120-124 1-181 CF₃ Pr-i Pr CH₂ 4-F O 126-127 1-182CF₃ Pr-i Me CH₂S H O 106-108 1-183 CF₃ Pr-i Me CH₂S 4-Cl O 111-113 1-184CClF₂ Pr-i Me O 4-F O 119-123 1-185 CClF₂ Pr-i Me O 4-Cl O  99-103 1-186CF₃ Ph Me CH₂ H O 86-87 1-187 CF₃ Ph Me CH₂ 4-Cl O 146-147 1-188 Bu-t MeMe CH₂ H O 1.5511 1-189 Bu-t Me Me CH₂ 4-F O 88-89 1-190 Bu-t Me Me CH₂4-Cl O 1.5582 1-191 Bu-t Me Me CH₂ 4-Me O 1.5471 1-192 CF₃ Pr-i MeCH(Me) 4-OMe O 1.5135 1-193 CF₃ Pr-i CH₂C≡CH CH₂ H O 117-121 1-194 CF₃Pr-i CH₂C≡CH CH₂ 4-Cl O 119-121 1-195 CF₃ Pr-i Me CH(Me) H O NotMeasurable 1-196 CF₃ Bu-t Me CH₂ H O 107-109 1-197 CF₃ Ph Me CH₂ 4-Me O151-154 1-198 CF₃ Pr-i Me CH(Me) 4-F O 1.4992 1-199 CF₃ Pr-i Me CH(Me)4-Me O 1-200 CF₃ 2-thienyl Me CH₂ 4-Cl O 120-121 1-201 SMe Bu-t Me CH₂ HO 1-202 SMe Bu-t Me CH₂ 4-F O 1-203 SMe Bu-t Me CH₂ 4-Cl O 1-204 SMeBu-t Me CH₂ 4-Me O 1-205 SMe Ph Me CH₂ H O 1-206 SMe Ph Me CH₂ 4-F O1-207 SMe Ph Me CH₂ 4-Cl O 1-208 SMe Ph Me CH₂ 4-Me O

 

TABLE 7 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1-209 Pr-i Bu-t Me CH₂ H O 1-210 Pr-i Bu-t MeCH₂ 4-F o 1-211 Pr-i Bu-t Me CH₂ 4-Cl O 1-212 Pr-i Bu-t Me CH₂ 4-Me O1-213 Pr-i Ph Me CH₂ H O 1-214 Pr-i Ph Me CH₂ 4-F O 90-91 1-215 Pr-i PhMe CH₂ 4-Cl O 1-216 Pr-i Ph Me CH₂ 4-Me O 1-217 CF₃ Ph(4-F) Me CH₂ H O111-112 1-218 CF₃ Ph(4-F) Me CH₂ 4-F O  99-101 1-219 CF₃ Ph(4-F) Me CH₂4-Cl O 137-139 1-220 CF₃ Ph(4-F) Me CH₂ 4-Me O 132-134 1-221 CF₃Ph(4-Cl) Me CH₂ H O 136-137 1-222 CF₃ Ph(4-Cl) Me CH₂ 4-F O 114-1151-223 CF₃ Ph(4-Cl) Me CH₂ 4-Cl O 1-224 CF₃ Ph(4-Cl) Me CH₂ 4-Me O 1-225CF₃ Ph(4-Me) Me CH₂ H O 1.5566 1-226 CF₃ Ph(4-Me) Me CH₂ 4-F O 1.55491-227 CF₃ Ph(4-Me) Me CH₂ 4-Cl O 1-228 CF₃ Ph(4-Me) Me CH₂ 4-Me O 1.55311-229 CF₃ 3-thienyl Me CH₂ H O 1-230 CF₃ 3-thienyl Me CH₂ 4-F O 1-231CF₃ 3-thienyl Me CH₂ 4-Cl O 1-232 CF₃ 3-thienyl Me CH₂ 4-Me O 1-233 CF₃2-thienyl Me CH₂ H O 1-234 CF₃ 2-thienyl Me CH₂ 4-F O  99-103 1-235 CF₃2-thienyl Me CH₂ 4-Cl O 1-236 CF₃ 2-thienyl Me CH₂ 4-Me O 1-237 CF₃Ph(3-Cl) Me CH₂ H O 1-238 CF₃ Ph(3-Cl) Me CH₂ 4-F O 1-239 CF₃ Ph(3-Cl)Me CH₂ 4-Cl O 1-240 CF₃ Ph(3-Cl) Me CH₂ 4-Me O 1-241 CF₃ Bu-t Me CH₂4-Br O 1-242 CF₃ Ph Me CH₂ 4-Br O 1-243 CF₃ Bu-s Me CH₂ 4-Br O 1-244CHF₂ Pr-i Me CH₂ 4-Br O

 

TABLE 8 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1-245 SMe Pr-i Me CH₂ 4-Br O 1-246 Pr-i Pr-iMe CH₂ 4-Br O 1-247 Pr-c Pr-i Me CH₂ 4-Br O 1-248 Me Bu-t Me CH₂ 4-Br O1-249 CF₃ Bu-t Me CH₂ 2-F,4-Cl O 101-103 1-250 CF₃ Ph Me CH₂ 2-F,4-Cl O170—173 1-251 CF₃ Bu-s Me CH₂ 2-F,4-Cl O 84-85 1-252 CHF₂ Pr-i Me CH₂2-F,4-Cl O 1-253 SMe Pr-i Me CH₂ 2-F,4-Cl O 1-254 Pr-i Pr-i Me CH₂2-F,4-Cl O 141-142 1-255 Pr-c Pr-i Me CH₂ 2-F,4-Cl O 1-256 Me Bu-t MeCH₂ 2-F,4-Cl O 1-257 CF₃ Bu-t Me CH₂ 3,4-(Me)₂ O 1-258 CF₃ Ph Me CH₂3,4-(Me)₂ O 1-259 CF₃ Bu-s Me CH₂ 3,4-(Me)₂ O 1-260 CHF₂ Pr-i Me CH₂3,4-(Me)₂ O 1-261 SMe Pr-i Me CH₂ 3,4-(Me)₂ O 1-262 Pr-i Pr-i Me CH₂3,4-(Me)₂ O 1-263 Pr-i Pr-c Me CH₂ 3,4-(Me)₂ O 1-264 Me Bu-t Me CH₂3,4-(Me)₂ O 1-265 CF₃ Bu-t Me CH₂ 3-F O 103-104 1-266 CF₃ Ph Me CH₂ 3-FO 88-90 1-267 CF₃ Bu-s Me CH₂ 3-F O 85-87 1-268 CHF₃ Pr-i Me CH₂ 3-F O1-269 SMe Pr-i Me CH₂ 3-F O 1-270 Pr-i Pr-i Me CH₂ 3-F O 151-153 1-271Pr-c Pr-i Me CH₂ 3-F O 1-272 Me Bu-t Me CH₂ 3-F O 1-273 CF₃ Bu-t Me CH₂2,4-F₂ O 137-140 1-274 CF₃ Ph Me CH₂ 2,4-F₂ O 107-110 1-275 CF₃ Bu-s MeCH₂ 2,4-F₂ O 1-276 CHF₂ Pr-i Me CH₂ 2,4-F₂ O 1-277 SMe Pr-i Me CH₂2,4-F₂ O 1-278 Pr-i Pr-i Me CH₂ 2,4-F₂ O 1-279 Pr-c Pr-i Me CH₂ 2,4-F₂ O1-280 Me Bu-t Me CH₂ 2,4-F₂ O

 

TABLE 9 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1-281 CF₃ Bu-t Me CH₂ 3-F,4-Cl O 1-282 CF₃ PhMe CH₂ 3-F,4-Cl O 1-283 CF₃ Bu-s Me CH₂ 3-F,4-Cl O 1-284 CHF₂ Pr-i MeCH₂ 3-F,4-Cl O 1-285 SMe Pr-i Me CH₂ 3-F,4-Cl O 1-286 Pr-i Pr-i Me CH₂3-F,4-Cl O 1-287 Pr-c Pr-i Me CH₂ 3-F,4-Cl O 1-288 Me Bu-t Me CH₂3-F,4-Cl O 1-289 CF₃ Bu-t Me CH₂ 3,4-F₃ O 1-290 CF₃ Ph Me CH₂ 3,4-F₃ O1-291 CF₃ Bu-s Me CH₂ 3,4-F₃ O 1-292 CHF₂ Pr-i Me CH₂ 3,4-F₃ O 1-293 SMePr-i Me CH₂ 3,4-F₃ O 1-294 Pr-i Pr-i Me CH₂ 3,4-F₃ O 1-295 Pr-c Pr-i MeCH₂ 3,4-F₃ O 1-296 Me Bu-t Me CH₂ 3,4-F₃ O 1-297 CF₃ Bu-t Me CH₂ 3,5-F₃O 1-298 CF₃ Ph Me CH₂ 3,5-F₃ O 1-299 CF₃ Bu-s Me CH₂ 3,5-F₃ O 1-300 CHF₂Pr-i Me CH₂ 3,5-F₃ O 1-301 SMe Pr-i Me CH₂ 3,5-F₃ O 1-302 Pr-i Pr-i MeCH₂ 3,5-F₃ O 1-303 Pr-c Pr-i Me CH₂ 3,5-F₃ O 1-304 Me Bu-t Me CH₂ 3,5-F₃O 1-305 CF₃ Bu-t Me CH₂ 4-CF₃ O 85-87 1-306 CF₃ Ph Me CH₂ 4-CF₃ O 92-931-307 CF₃ Bu-s Me CH₂ 4-CF₃ O 123-125 1-308 CHF₂ Pr-i Me CH₂ 4-CF₃ O1-309 SMe Pr-i Me CH₂ 4-CF₃ O 1-310 Pr-i Pr-i Me CH₂ 4-CF₃ O 139-1401-311 Pr-c Pr-i Me CH₂ 4-CF₃ O 1-312 Me Bu-t Me CH₂ 4-CF₃ O 1-313 CF₃Bu-t Me CH₂ 3-CF₃ O 1-314 CF₃ Ph Me CH₂ 3-CF₃ O 1-315 CF₃ Bu-s Me CH₂3-CF₃ O 1-316 CHF₂ Pr-i Me CH₂ 3-CF₃ O

 

TABLE 10 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1-317 SMe Pr-i Me CH₂ 3-CF₃ O 1-318 Pr-i Pr-iMe CH₂ 3-CF₃ O 1-319 Pr-c Pr-i Me CH₂ 3-CF₃ O 1-320 Me Bu-t Me CH₂ 3-CF₃O 1-321 CF₃ Pr-i Et CH₂ 2-F,4-Cl O 144-146 1-322 Ph Pr-i Me CH₂ H O82-84 1-323 Ph Pr-i Me CH₂ 4-F O 104-105 1-324 Ph Pr-i Me CH₂ 4-Cl O88-90 1-325 Ph Pr-i Me CH₂ 4-Me O 79-80 1-326 Pr-i Pr-i Me NH H O199-200 1-327 Pr-i Pr-i Me N(Me) H O 1.5384 1-328 CF₃ Pr-i Me C(═O) H O101-102 1-329 CF₃ Pr-i Me C(Me)₂ 4-Cl O Not Measurable 1-330 CF₃ Bu-i MeCH₂ H O 86-87 1-331 CF₃ Bu-i Me CH₂ 4-F O 97-98 1-332 CF₃ Pr-i OMe CH₂ HO 1.5071 1-333 CF₃ Pr-i OMe CH₂ 4-F O 59-62 1-334 CF₃ Bu-i Me CH₂ 3-F O93-94 1-335 CF₃ Pr-i Me C(═O) 4-Cl O 116-119 1-336 Pr-i Ph Et CH₂ 4-Me O1-337 CF₃ Ph(4-F) Et CH₂ H O 1-338 CF₃ Ph(4-F) Et CH₂ 4-F O 1-339 CF₃Ph(4-F) Et CH₂ 4-Cl O 1-340 CF₃ Ph(4-F) Et CH₂ 4-Me O 1-341 CF₃ Ph(4-Cl)Et CH₂ H O 1-342 CF₃ Ph(4-Cl) Et CH₂ 4-F O 1-343 CF₃ Ph(4-Cl) Et CH₂4-Cl O 1-344 CF₃ Ph(4-Cl) Et CH₂ 4-Me O 1-345 CF₃ Ph(4-Me) Et CH₂ H O1-346 CF₃ Ph(4-Me) Et CH₂ 4-F O 1-347 CF₃ Ph(4-Me) Et CH₂ 4-Cl O 1-348CF₃ Ph(4-Me) Et CH₂ 4-Me O 1-349 CF₃ 3-thienyl Et CH₂ H O 1-350 CF₃3-thienyl Et CH₂ 4-F O 1-351 CF₃ 3-thienyl Et CH₂ 4-Cl O 1-352 CF₃3-thienyl Et CH₂ 4-Me O

 

TABLE 11 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1-353 CF₃ 2-thienyl Et CH₂ H O 1-354 CF₃2-thienyl Et CH₂ 4-F O 1-355 CF₃ 2-thienyl Et CH₂ 4-Cl O 1-356 CF₃2-thienyl Et CH₂ 4-Me O 1-357 CF₃ Ph(3-Cl) Et CH₂ H O 1-358 CF₃ Ph(3-Cl)Et CH₂ 4-F O 1-359 CF₃ Ph(3-Cl) Et CH₂ 4-Cl O 1-360 CF₃ Ph(3-Cl) Et CH₂4-Me O 1-361 CF₃ Ph Me CH(Me) H O 1-362 CF₃ Ph Me CH(Me) 4-F O 1-363 CF₃Ph Me CH(Me) 4-Cl O 1-364 CF₃ Ph Me CH(Me) 4-Me O 1-365 CF₃ Ph(4-F) MeCH(Me) H O 1-366 CF₃ Ph(4-F) Me CH(Me) 4-F O 1-367 CF₃ Ph(4-F) Me CH(Me)4-Cl O 1-368 CF₃ Ph(4-F) Me CH(Me) 4-Me O 1-369 CF₃ Ph(4-Cl) Me CH(Me) HO 1-370 CF₃ Ph(4-Cl) Me CH(Me) 4-F O 1-371 CF₃ Ph(4-Cl) Me CH(Me) 4-Cl O1-372 CF₃ Ph(4-Cl) Me CH(Me) 4-Me O 1-373 Pr-i Pr-i Me CH(Me) H O 1-374Pr-i Pr-i Me CH(Me) 4-F O 1-375 Pr-i Pr-i Me CH(Me) 4-Cl O 1-376 Pr-iPr-i Me CH(Me) 4-Me O 1-377 SMe Pr-i Me CH(Me) H O 1-378 SMe Pr-i MeCH(Me) 4-F O 1-379 SMe Pr-i Me CH(Me) 4-Cl O 1-380 SMe Pr-i Me CH(Me)4-Me O 1-381 CF₃ 3-thienyl Me CH(Me) H O 1-382 CF₃ 3-thienyl Me CH(Me)4-F O 1-383 CF₃ 3-thienyl Me CH(Me) 4-Cl O 1-384 CF₃ 3-thienyl Me CH(Me)4-Me O 1-385 CF₃ Ph(3-Cl) Me CH(Me) H O 1-386 CF₃ Ph(3-Cl) Me CH(Me) 4-FO 1-387 CF₃ Ph(3-Cl) Me CH(Me) 4-Cl O 1-388 CF₃ Ph(3-Cl) Me CH(Me) 4-MeO 1-389 Me Bu-t Me CH(Me) H O

 

TABLE 12 m.p. (° C.) or refrac- Dia- tive Compound stereo- index No. R¹R² R³ Z Xn Q mer (n_(D) ²⁰) 1-390 Me Bu-t Me CH(Me) 4-F O 1-391 Me Bu-tMe CH(Me) 4-Cl O 1-392 Me Bu-t Me CH(Me) 4-Me O 1-393 CF₃ Bu-t Me CH(Me)H O 1-394 CF₃ Bu-t Me CH(Me) 4-F O 1-395 CF₃ Bu-t Me CH(Me) 4-Cl O 1-396CF₃ Bu-t Me CH(Me) 4-Me O 1-397 CF₃ 2-thienyl Me CH(Me) H O 1-398 CF₃2-thienyl Me CH(Me) 4-F O 1-399 CF₃ 2-thienyl Me CH(Me) 4-Cl O 1-400 CF₃2-thienyl Me CH(Me) 4-Me O 1-401 OMe Pr-i Me CH₂ H O 1.5439 1-402 OMePr-i Me CH₂ 4-F O 1.5332 1-403 OMe Pr-i Me CH₂ 4-Cl O 79-82 1-404 OMePr-i Me CH₂ 4-Me O 88-90 1-405 CF₃ Pr-i OMe CH₂ H O 1-406 CF₃ Pr-i OMeCH₂ 4-F O 1-407 CF₃ Pr-i OMe CH₂ 4-Cl O 1.5159 1-408 CF₃ Pr-i OMe CH₂4-Me O 1-409 CF₃ 1-MePr-e Me CH₂ H O 78-79 1-410 CF₃

Me CH₂ 4-F O 85-87 1-411 CF₃

Me CH₂ 4-Cl O 110-111 1-412 CF₃

Me CH₂ 4-Me O 88-89 1-413 CF₃ CH₂SMe Me CH₂ 4-F O 65-66 1-414 CF₃ CH₂SMeMe CH₂ 4-Cl O 94-95 1-415 CF₃ CH₂SMe Me CH₂ 4-Br O 109-110 1-416 CF₃CH(Me)SMe Me CH₂ 4-F O 118-119 1-417 CF₃ Pr-i Me CH₂ 2,3,4-F₃ O 167-1691-418 CF₃ Pr-i Me CH₂ 3,4,5-F₃ O 181-183 1-419 CF₃ 1-MePr-e Me CH₂ 3-F O100-101 1-420 CF₃ CH₂SMe Me CH₂ 3-F O 66-67 1-421 CF₃ CH₂SMe Me CH₂ 4-MeO 87-89 1-422 CF₃ CH₂SMe Me CH₂ 2-F- O 102-103 4-Cl

 

TABLE 13 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1-423 CF₃ Et Pr-i CH₂ 4-Cl O 1.5207 1-424 CF₃Pr-i Me N-Me H O 104-105 1-425 CF₃ Pr-i Me N-Et H O 63-65 1-426 CF₃ Pr-iMe N-Me 4-F O 84-85 1-427 CF₃ Pr-i Me N-Me 4-Cl O 106-108 1-428 CF₃ Pr-iMe N-Me 4-Me O 94-96 1-429 Pr-i Pr-i Me N-Me 4-F O 1.5216 1-430 Pr-iPr-i Me N-Me 4-Cl O 120-123 1-431 Pr-i Pr-i Me N-Me 4-Me O 93-94 1-432Et Pr-i Me CH₂ H O 97-98 1-433 Et Pr-i Me CH₂ 4-F O 93-95 1-434 Et Pr-iMe CH₂ 4-Cl O 110-111 1-435 Et Pr-i Me CH₂ 4-Me O 79-81 1-436 Pr-i Et MeCH₂ H O 1.5455 1-437 Pr-i Et Me CH₂ 4-F O 66-67 1-438 Pr-i Et Me CH₂4-Cl O 110-111 1-439 Pr-i Et Me CH₂ 4-Me O 98-99 1-440 CF₃ 3-thienyl MeCH₂ H O 1-441 CF₃ 3-thienyl Me CH₂ 4-F O 109-110 1-442 CF₃ 3-thienyl MeCH₂ 4-Cl O 135-138 1-443 CF₃ 3-thienyl Me CH₂ 4-Me O 125-128 1-444 CF₃Pr-i Me CH₂ 2,3,5-F₃ O 167-169 1-445 Pr-n Pr-i Me CH₂ H O 67-69 1-446Pr-n Pr-i Me CH₂ 4-F O 117-118 1-447 Pr-n Pr-i Me CH₂ 4-Cl O 122-1231-448 Pr-n Pr-i Me CH₂ 4-Me O 89-90 1-449 Pr-i Pr-n Me CH₂ H O 1.54021-450 Pr-i Pr-n Me CH₂ 4-F O 83-84 1-451 Pr-i Pr-n Me CH₂ 4-Cl O 78-791-452 Pr-i Pr-n Me CH₂ 4-Me O 94-95 1-453 CH(OEt)₂ Pr-i Me CH₂ H O1.5253 1-454 Pr-i CH(OEt)₂ Me CH₂ H O 1.5221 1-455 Pr-i CH(OEt)₂ Me CH₂4-F O 1.5101 1-456 Pr-i CH(OEt)₂ Me CH₂ 4-Cl O 1-457 Pr-i CH(OEt)₂ MeCH₂ 4-Me O 1-458 Pr-i CH(OEt)₂ Me OCH₂ H O 1.5191

 

TABLE 14 m. p. (° C.) or refractive Compound index No. R¹ R² R³ Z Xn QDiastereomer (n_(D) ²⁰) 1-459 CF₃ Pr-i Me N-Me 4-CN O 144-145 1-460 CF₃Pr-i Me N-Me 4-OMe O 1.5081 1-461 CF₃ Pr-i Me NHCH₂ H O  92-95 1-462Pr-i CH═NOMe Me CH₂ H O 1-463 Pr-i CH═NOMe Me CH₂ 4-F O 1.5309 1-464Pr-i CH═NOMe Me CH₂ 4-Cl O 1.5459 1-465 Pr-i CH═NOMe Me CH₂ 4-Me O1.5412 1-466 Pr-i CH═NOMe Me OCH₂ H O 1.5352 1-467 CH(OEt)₂ Pr-i Me OCH₂H O 1.5236 1-468 CH(OEt)₂ Pr-i Me CH₂ 4-F O 1.5135 1-469 CH(OEt)₂ Pr-iMe CH₂ 4-Cl O 1.5282 1-470 CH(OEt)₂ Pr-i Me CH₂ 4-Me O 116-117 1-471CH═NOMe Pr-i Me OCH₂ H O 1.5481 1-472

Me CH₂ H O 1-473

Me CH₂ 4-F O 110-112 1-474

Me CH₂ 4-Cl O 1-475

CH₂CO₂Et CH₂ 4-Me O 1-476 CF₃ Pr-i CH₂CO₂Et CH₂ H O 158-159 1-477 CF₃Pr-i CH₂CO₂Et CH₂ 4-F O 1-478 CF₃ Pr-i CH₂CO₂Et CH₂ 4-Cl O 1-479 CF₃Pr-i CH₂CO₂Et CH₂ 4-Me O 1-480 CF₃ Pr-i CH₂CN CH₂ H O 1-481 CF₃ Pr-iCH₂CN CH₂ 4-F O 1-482 CF₃ Pr-i CH₂CN CH₂ 4-Cl O 164-166 1-483 CF₃ Pr-iCH₂CN CH₂ 4-Me O 159-161 1-484 CF₃ Ph(4-OMe) Me CH₂ H O  97-98 1-485 CF₃Ph(4-OMe) Me CH₂ 4-F O 103-105 1-486 CF₃ Ph(4-OMe) Me CH₂ 4-Cl O 131-1331-487 CF₃ Ph(4-OMe) Me CH₂ 4-Me O 147-150 1-488 CF₃ Ph(2-OMe) Me CH₂ H ONot Measurable

 

TABLE 15 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1-489 CF₃ Ph(2-OMe) Me CH₂ 4-F O 1.5474 1-490CF₃ Ph(2-OMe) Me CH₂ 4-Cl O Not Measurable 1-491 CF₃ Ph(2-OMe) Me CH₂4-Me O 1.5432 1-492 Pr-n Pr-n Me CH₂ H O 65-66 1-493 Pr-n Pr-n Me CH₂4-F O 83-84 1-494 Pr-n Pr-n Me CH₂ 4-Cl O 91-92 1-495 Pr-n Pr-n Me CH₂4-Me O 55‥56 1-496 CH═NOMe Pr-i Me CH₂ H O 113-115 1-497 CH═NOMe Pr-i MeCH₂ 4-F O 155-156 1-498 CH═NOMe Pr-i Me CH₂ 4-Cl O 122-123 1-499 CH═NOMePr-i Me CH₂ 4-Me O 1.5468 1-500 CH═NOH Pr-i Me CH₂ H O 171-172 1-501CH═NOH Pr-i Me CH₂ 4-F O 197-198 1-502 CH═NOH Pr-i Me CH₂ 4-Cl O 183-1841-503 CH═NOH Pr-i Me CH₂ 4-Me O 155-157 1-504 CN Pr-i Me CH₂ H O 80-811-505 CN Pr-i Me CH₂ 4-F O 105-106 1-506 CN Pr-i Me CH₂ 4-Cl O  99-1001-507 CN Pr-i Me CH₂ 4-Me O 75-76 1-508 CN Pr-i Me CH(Me) 4-Cl O 1.66691-509 Pr-i CMe(OMe)₂ Me CH₂ H O 1.5352 1-510 Pr-i CMe(OMe)₂ Me CH₂ 4-F O112-113 1-511 Pr-i CMe(OMe)₂ Me CH₂ 4-Cl O 106-107 1-512 Pr-i CMe(OMe)₂Me CH₂ 4-Me O 104-105 1-513 Pr-i COMe Me CH₂ H O  99-100 1-514 Pr-i COMeMe CH₂ 4-F O 114-115 1-515 Pr-i COMe Me CH₂ 4-Cl O 108-109 1-516 Pr-iCOMe Me CH₂ 4-Me O 119-120 1-517 CMe(OMe)₂ Pr-i Me CH₂ 4-Cl O 78-791-518 CF₃ Pr-i CH₂CH═CH₂ CH₂ H O 121-122 1-519 CF₃ Pr-i CH₂CH═CH₂ CH₂4-F O 129-130 1-520 CF₃ Pr-i CH₂CH═CH₂ CH₂ 4-Cl O 124-127 1-521 CF₃ Pr-iCH₂CH═CH₂ CH₂ 4-Me O 98-99 1-522 CHO Pr-i Me CH₂ H O 1-523 CHO Pr-i MeCH₂ 4-F O 1.5466 1-524 CHO Pr-i Me CH₂ 4-Cl O 1.5609

 

TABLE 16 m. p. (° C.) or refractive Compound index No. R¹ R² R³ Z Xn QDiastereomer (n_(D) ²⁰) 1-525 CHO Pr-i Me CH₂ 4-Me O 1.5558 1-526 COMePr-i Me CH₂ H O Not Measurable 1-527 COMe Pr-i Me CH₂ 4-F O 1.5341 1-528COMe Pr-i Me CH₂ 4-Cl O 1.5501 1-529 COMe Pr-i Me CH₂ 4-Me O 1.54231-530 COMe Pr-i Me CH(Me) 4-Cl O 1.5395 1-531 Pr-i CH═NOH Me OCH₂ H O1.5365 1-532 CF₃ Pr-i Me N(Me)CH₂ 4-Cl O  95-96 1-533 CF₃ Pr-i MeN(CH₂C≡CH) 4-F O 1.5121 1-534 CF₃ Pr-i Me NHCH(Me) H O  69-70 (R-isomer)1-535 CF₃ Pr-i Me NHCH(Me) H O 1.5134 (S-isomer) 1-536 CF₃ Pr-i Me N(Me)2-F O 1.5043 1-537 CF₃ Pr-i Me N(Me) 2,4-F₂ O 1.4936 1-538 Et Pr-i MeN(Me) H O 1.5451 1-539 Et Pr-i Me N(Me) 4-F O 1.5349 1-540 Et Pr-i MeN(Me) 4-Cl O 115-117 1-541 Et Pr-i Me N(Me) 4-Me O 1.5342 1-542 CF₃ Pr-i

CH₂ H O 1.5131 1-543 CF₃ Pr-i

CH₂ 4-F O 1.5052 1-544 CF₃ Pr-i

CH₂ 4-Cl O 1.5215 1-545 CF₃ Pr-i

CH₂ 4-Me O 1.5121 1-546 CF₃ Ph(2-F) Me CH₂ H O 109-110 1-547 CF₃ Ph(2-F)Me CH₂ 4-F O 107-108 1-548 CF₃ Ph(2-F) Me CH₂ 4-Cl O 139-141 1-549 CF₃Ph(2-F) Me CH₂ 4-Me O 107-110 1-550 CF₃ Ph(2-Me) Me CH₂ H O 146-1471-551 CF₃ Ph(2-Me) Me CH₂ 4-F O 149-150 1-552 CF₃ Ph(2-Me) Me CH₂ 4-Cl1-553 CF₃ Ph(2-Me) Me CH₂ 4-Me O 135-136

 

TABLE 17 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1.554 CF₃ Ph(2,4-F₂) Me CH₂ H O 1.555 CF₃Ph(2,4-F₂) Me CH₂ 4-F O 102-104 1-556 CF₃ Ph(2,4-F₂) Me CH₂ 4-Cl O 1-557CF₃ Ph(2,4-F₂) Me CH₂ 4-Me O 1-558 Et Pr-i CH₂C≡CH CH₂ H O 131-132 1-559Et Pr-i CH₂C≡CH CH₂ 4-F O 93-96 1-560 Et Pr-i CH₂C≡CH CH₂ 4-Cl O 124-1251-561 Et Pr-i CH₂C≡CH CH₂ 4-Me O 110-111 1-562 Et Pr-i CH₂C≡CH CH(Me) HO Not Measurable 1-563 Pr-i C(Me)═NOMe Me CH₂ 4-F O 73-74 1-564 Et Bu-tMo CH₂ H O 1-565 Et Bu-t Me CH₂ 4-F O 82-83 1-566 Et Bu-t Me CH₂ 4-Cl O98-99 1-567 Et Bu-t Me CH₂ 4-Me O 78-80 1-568 Pr-i CN Me OCH₂ H O 1.58991-569 CF₃ Pr-i CH₂C≡CH CH₂ 3-F O 131-133 1-570 Bu-t Et Me CH₂ H O 1-571Bu-t Et Me CH₂ 4-F O 88-90 1-572 Bu-t Et Me CH₂ 4-Cl O 96-97 1-573 Bu-tEt Me CH₂ 4-Me O 101-102 1-574 CF₃ Pr-i CH₂-Pr-c CH₂ H O 1-575 CF₃ Pr-iCH₂-Pr-c CH₂ 4-F O 108-109 1-576 CF₃ Pr-i CH₂-Pr-c CH₂ 4-Cl O 1-577 CF₃Pr-i CH₂-Pr-c CH₂ 4-Me O 1-578 CF₃ Pr-i CH₂CN CH₂ H O 1-579 CF₃ Pr-iCH₂CN CH₂ 4-F O 162-163 1-580 CF₃ Pr-i CH₂CN CH₂ 4-Cl O 1-581 CF₃ Pr-iCH₂CN CH₂ 4-Me O 1-582 Pr-i CH₂OMe Me CH₂ H O 1-583 Pr-i CH₂OMe Me CH₂4-F O 1-584 Pr-i CH₂OMe Me CH₂ 4-Cl O 1.5391 1-585 Pr-i CH₂OMe Me CH₂4-Me O 1-586 Pr-i CH₂OMe Me CH(Me) 4-Cl O 1.5358 1-587 CH₂OMe Pr-i MeCH₂ H O 1-588 CH₂OMe Pr-i Me CH₂ 4-F O 1-589 CH₂OMe Pr-i Me CH₂ 4-Cl O1.5485

 

TABLE 18 m. p. (° C.) or refractive Compound index No. R¹ R² R³ Z Xn QDiastereomer (n_(D) ²⁰) 1-590 CH₂OMe Pr-i Me CH₂ 4-Me O 1-591 CH₂OMePr-i Me CH(Me) 4-Cl O 1.5382 1-592 CO₂Me Pr-i Me CH(Me) 4-Cl O A-isomerNot Measurable 1-593 CO₂Me Pr-i Me CH(Me) 4-Cl O B-isomer Not Measurable1-594 CO₂Et Pr-i Me CH(Me) 4-Cl O A-isomer 1.5406 1-595 CO₂Et Pr-i MeCH(Me) 4-Cl O B-isomer Not Measurable 1-596

Pr-i Me CH₂ H O 1-597

Pr-i Me CH₂ 4-F O 171-173 1-598

Pr-i Me CH₂ 4-Cl O 167-168 1-599

Pr-i Me CH₂ 4-Me O 141-142 1-600 Pr-i

Me CH(Me) 4-Cl O  95-98 1-601 Pr-i

Me CH₂ H O 1-602 Pr-i

Me CH₂ 4-F O 123-124 1-603 Pr-i

Me CH₂ 4-Cl O 133-134 1-604 Pr-i

Me CH₂ 4-Me O 103-104 1-605 Pr-i

Me CH(Me) 4-Cl O 1-606 Et Pr-n CH₂C≡CH CH₂ H O  58-59 1-607 Et Pr-nCH₂C≡CH CH₂ 4-F O  76-77 1-608 Et Pr-n CH₂C≡CH CH₂ 4-Cl O 111-113 1-609Et Pr-n CH₂C≡CH CH₂ 4-Me O  90-91 1-610 Pr-i Pr-n CH₂C≡CH CH₂ H O 1-611Pr-i Pr-n CH₂C≡CH CH₂ 4-F O  70-71 1-612 Pr-i Pr-n CH₂C≡CH CH₂ 4-Cl O

 

TABLE 19 Dia- m.p. (° C.) Compound stereo- or refractive No. R¹ R² R³ ZXn Q mer index (n_(D) ²⁰) 1-613 Pr-n Pr-i CH₂C≡CH CH₂ 4-Me O 1-614 CF₃Pr-i CH₂C≡CH CH₂ 3,4-F₂ O 133-134 1-615 CF₃ Pr-i CH₂C≡CH CH₂ 2-F-4-Cl O122-124 1-616 Pr-n Pr-i CH₂C≡CH CH₂ H O 118-119 1-617 Pr-n Pr-i CH₂C≡CHCH₂ 4-F O 106-107 1-618 Pr-n Pr-i CH₂C≡CH CH₂ 4-Cl O 111-112 1-619 Pr-nPr-i CH₂C≡CH CH₂ 4-Me O 98-99 1-620 CF₃ Bu-t CH₂C≡CH CH₂ 4-F O 93-961-621 Pr-i Pr-i CH₂C≡CH CH₂ H O 137-138 1-622 Pr-i Pr-i CH₂C≡CH CH₂ 4-FO 159-161 1-623 Pr-i Pr-i CH₂C≡CH CH₂ 4-Cl O 131-134 1-624 Pr-i Pr-iCH₂C≡CH CH₂ 4-Me O 153-154 1-625 CH(OMe)₂ Pr-i Me CH(Me) 4-Cl O 1.53711-626 Et Bu-t CH₂C≡CH CH₂ H O 84-88 1-627 Et Bu-t CH₂C≡CH CH₂ 4-F O127-130 1-628 Et Bu-t CH₂C≡CH CH₂ 4-Cl O 1-629 Et Bu-t CH₂C≡CH CH₂ 4-MeO 1-630 COPr-i Pr-i Me CH(Me) 4-Cl O 116-117 1-631 C(Me)═NOMe Pr-i MeCH(Me) 4-Cl O 1.5423 1-632 CN Bu-t Me CH(Me) 4-Cl O A-isomer 130-1321-633 COMe Bu-t Me CH(Me) 4-Cl O 1.5439 1-634 CF₃ Pr-i Me CH(Me) H OA-isomer 128-131 (S-isomer) 1-635 CF₃ Pr-i Me CH(Me) H O B-isomer 1.5091(S-isomer) 1-636 CF₂Cl Pr-i Me O 4-Me O 112-115 1-637 CF₂Cl Pr-i Me O4-OMe O 123-126 1-638 CF₂Cl Pr-i Me O 4-Br O 108-111 1-639 CF₂Cl Pr-i MeOCH₂ H O 1.5251 1-640 CF₂Cl Pr-i Me O 4-NO₂ O 1.5301 1-641 CF₂Cl Pr-i MeO H S 132-135 1-642 Et Pr-i Me O 4-Cl O 80-83 1-643 Pr-n Pr-n Me O 4-ClO 1.5379 1-644 Pr-n Pr-i Me O 4-Cl O 1.5367 1-645 Me Me Me O 4-Cl O90-93 1-646 Et Et Me O 4-Cl O 1.5468

 

TABLE 20 m.p. (° C.) or Dia- refractive Compound stereo- index No. R¹ R²R³ Z Xn Q mer (n_(D) ²⁰) 1-647 Pr-i Pr-i Me O H O 1.5331 1-648 Pr-i Pr-iMe O 4-Me O 1.5346 1-649 Pr-i Pr-i Me O 4-OMe O 1.5282 1-650 Pr-i Pr-iMe O 4-F P 1.5169 1-651 Et CH(Me)SMe Me CH₂ H O Not Measurable 1-652 EtCH(Me)SMe Me CH₂ 4-F O Not Measurable 1-653 Et CH(Me)SMe Me CH₂ 4-Cl O88-91 1-654 Et CH(Me)SMe Me CH₂ 4-Me O 1.5676 1-655 NHCO₂CH₃Ph Pr-i MeCH(Me) 4-Cl O 161-163 1-656 Et C(Me)₂CO₂Me Me CH₂ 4-Cl O 1.5502 1-657SOMe Pr-i Me CH₂ 4-Cl O 1-658 SO₂Me Pr-i Me CH₂ 4-Cl O 1-659 OEt Pr-i MeCH₂ H O 1-660 OEt Pr-i Me CH₂ 4-F O 1-661 OEt Pr-i Me CH₂ 4-Cl O 1-662OEt Pr-i Me CH₂ 4-Me O 1-663 OCHF₂ Pr-i Me CH₂ H O 1-664 OCHF₂ Pr-i MeCH₂ 4-F O 1-655 OCHF₂ Pr-i Me CH₂ 4-Cl O 1-666 OCHF₂ Pr-i Me CH₂ 4-Me O1-667 SOCH₂CH═CH₂ Pr-i Me CH₂ 4-Cl O 1-668 SOCH₂C≡CH Pr-i Me CH₂ 4-Cl O1-669 OCH₂CH≡CH₂ Pr-i Me CH₂ H O 1-670 OCH₂CH═CH₂ Pr-i Me CH₂ 4-F O1-671 OCH₂CH═CH₂ Pr-i Me CH₂ 4-Cl O 1-672 OCH₂CH═CH₂ Pr-i Me CH₂ 4-Me O1-673 OCH₂C≡CH Pr-i Me CH₂ H O 1-674 OCH₂C≡CH Pr-i Me CH₂ 4-F O 1-675OCH₂C≡CH Pr-i Me CH₂ 4-Cl O 1-676 OCH₃C≡CH Pr-i Me CH₂ 4-Me O 1-677OPr-c Pr-i Me CH₂ H O 1-678 OPr-c Pr-i Me CH₂ 4-F O 1-679 OPr-c Pr-i MeCH₂ 4-Cl O 1-680 OPr-c Pr-i Me CH₂ 4-Me O 1-681 SPr-c Pr-i Me CH₂ 4-Cl O

 

TABLE 21 m.p. (° C.) or Dia- refractive Compound stereo- index No. R¹ R²R³ Z Xn Q mer (n_(D) ²⁰) 1-682 SOPr-c Pr-i Me CH₂ 4-Cl O 1-683 SO₂Pr-cPr-i Me CH₂ 4-Cl O 1-684 N(Me)₂ Pr-i Me CH₂ 4-Cl O 1-685 NHMe Pr-i MeCH₂ 4-Cl O 1-686 NH(CHF₂) Pr-i Me CH₂ 4-Cl O 1-687 NH(CH₂OMe) Pr-i MeCH₂ 4-Cl O 1-688 NH(CH₂SMe) Pr-i Me CH₂ 4-Cl O 1-689 NHPr-c Pr-i Me CH₂4-Cl O 1-690 NHCOMe Pr-i Me CH₂ 4-Cl O 1-691 NHSO₂Me Pr-i Me CH₂ 4-Cl O1-692 NHCO₂Me Pr-i Me CH₂ 4-Cl O 1-693 NH(CH₂CH═CH₂) Pr-i Me CH₂ 4-Cl O1-694 NH(CH₂C≡CH) Pr-i Me CH₂ 4-Cl O 1-695 CH(Me)CH═CH₂ Pr-i Me CH₂ 4-ClO 1-696 CH₂C≡CH Pr-i Me CH₂ 4-Cl O 1-697 OH Pr-i Me CH₂ 4-Cl O 1-698CO₂H Pr-i Me CH₂ 4-Cl O 1-699 CON(—C₄H₈) Pr-i Me CH₂ 4-Cl O 1-700CONH(CH₂CH═CH₂) Pr-i Me CH₂ 4-Cl O 1-701 Pr-i CH(Me)CH═CH₂ Me CH₂ 4-Cl O1-702 Pr-i CH₂C≡CH Me CH₂ 4-Cl O 1-703 Et CHClMe Me CH₂ 4-Cl O 1-704 EtOEt Me CH₂ 4-Cl O 1-705 Et CH(Me)CN Me CH₂ 4-Cl O 1-706 Et CO₂Me Me CH₂4-Cl O 1-707 Et CHMeN(Me)₂ Me CH₂ 4-Cl O 1-708 Et CON(Me)₂ Me CH₃ 4-Cl O1-709 Et CHMeCONMe₂ Me CH₂ 4-Cl O 1-710 Et Pr-i Me CH₂ 4-OCH₂CH═CH₂ O1-711 Et Pr-i Me CH₂ 4-OPr-c O 1-712 Et Pr-i Me CH₂ 4-COMe O

 

TABLE 22 m.p. (° C.) or Dia- refractive Compound stereo- index No. R¹ R²R³ Z Xn Q mer (n_(D) ²⁰) 1-713 Et Pr-i Me CH₂ 4-CO₂Me O 1-714 Et Pr-i MeCH₂ 4-SOMe O 1-715 Et Pr-i N(NMe₂) CH₂ 4-Cl O 1-716 Et Pr-i Me CH₂4-CH₂CH═CH₂ O 1-717 Et Pr-i Me CH₂ 4-CH₂C≡CH O 1-718 CO₂H Pr-i N(Me)CH(Me) 4-Cl O 168-170 1-719 CH═CHCO₂Et Pr-i Me CH(Me) 4-Cl O 57-59 1-720CF₃ Pr-i CH₂C≡CH CH₂ 4-Me O 111-113 1-721 COEt Pr-i Me CH(Me) H O 1-722COEt Pr-i Me CH(Me) 4-F O 1-723 COEt Pr-i Me CH(Me) 4-Cl O 1-724 COEtPr-i Me CH(Me) 4-Me O 1-725 COEt Pr-n Me CH₂ H O 1-726 COEt Pr-n Me CH₂4-F O 1-727 COEt Pr-n Me CH₂ 4-Cl O 1-728 COEt Pr-n Me CH₂ 4-Me O 1-729COEt Pr-i CH₂C≡CH CH(Me) H O 1-730 COEt Pr-i CH₂C≡CH CH(Me) 4-F O 1-731COEt Pr-i CH₂C≡CH CH(Me) 4-Cl O 1-732 COEt Pr-i CH₂C≡CH CH(Me) 4-Me O1-733 COEt Pr-n CH₂C≡CH CH₂ H O 1-734 COEt Pr-n CH₂C≡CH CH₂ 4-F O 1-735COEt Pr-n CH₂C≡CH CH₂ 4-Cl O 1-736 COEt Pr-n CH₂C≡CH CH₂ 4-Me O 1-737COMe Pr-n Me CH₂ H O 1-738 COMe Pr-n Me CH₂ 4-F O 1-739 COMe Pr-n Me CH₂4-Cl O 1-740 COMe Pr-n Me CH₂ 4-Me O 1-741 COMe Pr-i CH₂C≡CH CH(Me) H O1-742 COMe Pr-i CH₂C≡CH CH(Me) 4-F O 1-743 COMe Pr-i CH₂C≡CH CH(Me) 4-ClO 1-744 COMe Pr-i CH₂C≡CH CH(Me) 4-Me O 1-745 COMe Pr-n CH₂C≡CH CH₂ H O1-746 COMe Pr-n CH₂C≡CH CH₂ 4-F O 1-747 COMe Pr-n CH₂C≡CH CH₂ 4-Cl O1-748 COMe Pr-n CH₂C≡CH CH₂ 4-Me O

 

TABLE 23 m.p. (° C.) or Dia- refractive Compound stereo- index No. R¹ R²R³ Z Xn Q mer (n_(D) ²⁰) 1-749 COPr-i Pr-i Me CH(Me) H O 1-750 COPr-iPr-i Me CH(Me) 4-F O 1-751 COPr-i Pr-i Me CH(Me) 4-Me O 1-752 COPr-iPr-n Me CH₂ H O 1-753 COPr-i Pr-n Me CH₂ 4-F O 1-754 COPr-i Pr-n Me CH₂4-Cl O 1-755 COPr-i Pr-n Me CH₂ 4-Me O 1-756 COPr-i Pr-i CH₂C≡CH CH(Me)H O 1-757 COPr-i Pr-i CH₂C≡CH CH(Me) 4-F O 1-758 COPr-i Pr-i CH₂C≡CHCH(Me) 4-Cl O 1-759 COPr-i Pr-i CH₂C≡CH CH(Me) 4-Me O 1-760 COPr-i Pr-nCH₂C≡CH CH₂ H O 1-761 COPr-i Pr-n CH₂C≡CH CH₂ 4-F O 1-762 COPr-i Pr-nCH₂C≡CH CH₂ 4-Cl O 1-763 COPr-i Pr-n CH₂C≡CH CH₂ 4-Me O 1-764 OEt Pr-nMe CH₂ H O 1-765 OEt Pr-n Me CH₂ 4-F O 1-766 OEt Pr-n Me CH₂ 4-Cl O1-767 OEt Pr-n Me CH₂ 4-Me O 1-768 OEt Pr-i CH₂C≡CH CH(Me) H O 1-769 OEtPr-i CH₂C≡CH CH(Me) 4-F O 1-770 OEt Pr-i CH₂C≡CH CH(Me) 4-Cl O 1-771 OEtPr-i CH₂C≡CH CH(Me) 4-Me O 1-772 OPr-i Pr-i Me CH(Me) H O 1-773 OPr-iPr-i Me CH(Me) 4-F O 1-774 OPr-i Pr-i Me CH(Me) 4-Cl O 1-775 OPr-i Pr-iMe CH(Me) 4-Me O 1-776 OPr-i Pr-n Me CH₂ H O 1-777 OPr-i Pr-n Me CH₂ 4-FO 1-778 OPr-i Pr-n Me CH₂ 4-Cl O 1-779 OPr-i Pr-n Me CH₂ 4-Me O 1-780OPr-i Pr-i CH₂C≡CH CH(Me) H O 1-781 OPr-i Pr-i CH₂C≡CH CH(Me) 4-F O1-782 OPr-i Pr-i CH₂C≡CH CH(Me) 4-Cl O 1-783 OPr-i Pr-i CH₂C≡CH CH(Me)4-Me O 1-784 Et Ph Me CH₂ H O 1-785 Et Ph Me CH₂ 4-F O

 

TABLE 24 m.p. (° C.) or Dia- refractive Compound stereo- index No. R¹ R²R³ Z Xn Q mer (n_(D) ²⁰) 1-786 Et Ph Me CH₂ 4-Cl O 1-787 Et Ph Me CH₂4-Me O 1-788 N(Me)₂ Pr-i Me CH₂ H O 63-66 1-789 N(Me)₂ Pr-i Me CH₂ 4-F O1-790 N(Me)₂ Pr-i Me CH₂ 4-Me O 1-791 N(Me)₂ Pr-i Me CH(Me) H O 1-792N(Me)₂ Pr-i Me CH(Me) 4-F O 1-793 N(Me)₂ Pr-i Me CH(Me) 4-Cl O 1-794N(Me)₂ Pr-i Me CH(Me) 4-Me O 1-795 CF₃ Pr-i Me N(Me)CH₂ H O 1-796 CF₃Pr-i Me N(Me)CH₂ 4-F O 1-797 CF₃ Pr-i Me N(Me)CH₂ 4-Me O 1-798 Et Pr-iMe N(Me)CH₂ H O 1-799 Et Pr-i Me N(Me)CH₂ 4-F O 1-800 Et Pr-i MeN(Me)CH₂ 4-Cl O 1-801 Et Pr-i Me N(Me)CH₂ 4-Me O 1-802 Pr-i Pr-i MeN(Me)CH₂ H O 1-803 Pr-i Pr-i Me N(Me)CH₂ 4-F O 1-804 Pr-i Pr-i MeN(Me)CH₂ 4-Cl O 1-805 Pr-i Pr-i Me N(Me)CH₂ 4-Me O 1-806 C(Me)═CH₂ Pr-nMe CH₂ H O 1-807 C(Me)═CH₂ Pr-n Me CH₂ 4-F O 1-808 C(Me)═CH₂ Pr-n Me CH₂4-Cl O 1-809 C(Me)═CH₂ Pr-n Me CH₂ 4-Me O 1-810 Pr-n C(Me)═CH₂ Me CH₂ HO 1-811 Pr-n C(Me)═CH₂ Me CH₂ 4-F O 1-812 Pr-n C(Me)═CH₂ Me CH₂ 4-Cl O1-813 Pr-n C(Me)═CH₂ Me CH₂ 4-Me O 1-814 Et C(Me)═CH₂ Me CH₂ H O 1-815Et C(Me)═CH₂ Me CH₂ 4-F O 1-816 Et C(Me)═CH₂ Me CH₂ 4-Cl O 1-817 EtC(Me)═CH₂ Me CH₂ 4-Me O 1-818 Et OEt Me CH(Me) 4-Cl O 1-819 Et CH(Me)CNMe CH(Me) 4-Cl O 1-820 Et CO₂Me Me CH(Me) 4-Cl O 1-821 Et CHMeN(Me)₂ MeCH(Me) 4-Cl O

 

TABLE 25 m.p. (° C.) or Dia- refractive Compound stereo- index No. R¹ R²R³ Z Xn Q mer (n_(D) ²⁰) 1-822 Et CON(Me)₂ Me CH(Me) 4-Cl O 1-823 EtCHMeCONMe₂ Me CH(Me) 4-Cl O 1-824 Bu-t Et CH₂C≡CH CH₂ H O 1-825 Bu-t EtCH₂C≡CH CH₂ 4-F O 1-826 Bu-t Et CH₂C≡CH CH₂ 4-Cl O 1-827 Bu-t Et CH₂C≡CHCH₂ 4-Me O 1-828 COPr-c Pr-n Me CH₂ H O 1-829 COPr-c Pr-n Me CH₂ 4-F O1-830 COPr-c Pr-n Me CH₂ 4-Cl O 1-831 COPr-c Pr-n Me CH₂ 4-Me O 1-832 EtC(Me)₂OH Me CH₂ H O 1-833 Et C(Me)₂OH Me CH₂ 4-F O 1-834 Et C(Me)₂OH MeCH₂ 4-Cl O 1-835 Et C(Me)₂OH Me CH₂ 4-Me O 1-836 Et C(Me)₂Cl Me CH₂ H O1-837 Et C(Me)₂Cl Me CH₂ 4-F O 1-838 Et C(Me)₂Cl Me CH₂ 4-Cl O 1-839 EtC(Me)₂Cl Me CH₂ 4-Me O 1-840 N(Me)CH₂C≡CH Pr-i Me CH₂ H O 1-841N(Me)CH₂C≡CH Pr-i Me CH₂ 4-F O 1-842 N(Me)CH₂C≡CH Pr-i Me CH₂ 4-Cl O1-843 N(Me)CH₂C≡CH Pr-i Me CH₂ 4-Me O 1-844 N(Me)CH₂C≡CH Pr-i Me CH(Me)H O 1-845 N(Me)CH₂C≡CH Pr-i Me CH(Me) 4-F O 1-846 N(Me)CH₂C≡CH Pr-i MeCH(Me) 4-Cl O 1-847 N(Me)CH₂C≡CH Pr-i Me CH(Me) 4-Me O 1-848 CH₂CF₃ Pr-iMe CH₂ H O 1-849 CH₂CF₃ Pr-i Me CH₂ 4-F O 1-850 CH₂CF₃ Pr-i Me CH₂ 4-ClO 1-851 CH₂CF₃ Pr-i Me CH₂ 4-Me O 1-852 CF₂CF₃ Pr-i Me CH₂ H O 106-1081-853 CF₂CF₃ Pr-i Me CH₂ 4-F O 118-119 1-854 CF₂CF₃ Pr-i Me CH₂ 4-Cl O122-123 1-855 CF₂CF₃ Pr-i Me CH₂ 4-Me O 68-69 1-856 OCF₃ Pr-i Me CH₂ H O1-857 OCF₃ Pr-i Me CH₂ 4-F O

 

TABLE 26 m. p. (° C.) or refractive Compound index No. R¹ R² R³ Z Xn QDiastereomer (n_(D) ²⁰) 1-858 OCF₃ Pr-i Me CH₂ 4-Cl O 1-859 OCF₃ Pr-i MeCH₂ 4-Me O 1-860 Et CH(Me)OMe Me CH₂ H O 1-861 Et CH(Me)OMe Me CH₂ 4-F O1-862 Et CH(Me)OMe Me CH₂ 4-Cl O 1-863 Et CH(Me)OMe Me CH₂ 4-Me O 1-864Et CH(Me)CN Me CH₂ H O 1-865 Et CH(Me)CN Me CH₂ 4-F O 1-866 Et CH(Me)CNMe CH₂ 4-Me O 1-867 Et Pr-i CH₂C≡CH CH₂ 3,4-F₂ O 1-868 Et Pr-i CH₂C≡CHCH₂ 2,4-F₂ O 1-869 Et Pr-i CH₂C≡CH CH₂ 3-F O 1-870 CF₃ Pr-i CH₂C≡CH CH₂2,4-F₂ O λ-isomer 110-113 1-871 CF₃ Pr-i Me CH(Me) H O B-isomer 144-146(R-isomer) 1-872 CF₃ Pr-i Me CH(Me) H O 1.5164 (R-isomer) 1-873 CClF₂Pr-i Me N(Me) H O 1.5341 1-874 CF₃ Pr-i Me NHN(Me) H O  72-75 1-875CH₂CH(OMe)₂ Pr-i Me CH₂ 4-Cl O  90-91 1-876 CH₂CN Pr-i Me CH₂ 4-Cl O106-107 1-877

Et Me CH₂ 4-Cl O 1.5552 1-878 COMe Et Me CH₂ 4-Cl O 1.5612 1-879CMe═NOMe Et Me CH₂ 4-Cl O  81-83 1-880 CF₃ Pr-i Me N(Me)CH₂ H O  63-641-881 CH═NOMe Pr-n Me CH(Me) 4-Cl O Not Measurable 1-882 CN Pr-n MeCH(Me) 4-Cl O 103-106 1-883 Et

Me CH₂ 4-Cl O 161-162 1-884 Et CMe(OMe)₂ Me CH₂ H O Not Measurable 1-885Et CMe═NOMe Me CH₂ H O Not Measurable 1-886 Et CMe(OMe)₂ Me CH₂ 4-F ONot Measurable 1-887 Et COMe Me CH₂ 4-F O  71-73 1-888 Et CMe═NOMe MeCH₂ 4-F O 1.5443 1-889 COOH Pr-i Me CH₂ 4-Cl O 139-141 1-890 CN Bu-t MeCHMe 4-Cl O 106-108

 

TABLE 27

m. p. (° C.) or refractive Compound index No. R¹ R² R³ Z Ar Q (n_(D) ²⁰)2-1  CF₃ Pr-i Me CH₂ 2-napthyl O 137-138 2-2  CF₃ Pr-i Me CH₂ 3-thienylO  37-38 2-3  CF₃ Pr-i Me CH₂ 2-pyridyl O  99-100 2-4  CF₃ Pr-i Me CH₂3-pyridyl O  93-96 2-5  CF₃ Pr-i Me CH₂ 4-pyridyl O 115-118 2-6  CF₃Pr-i Me CH₂ 2-thienyl O  51-54 2-7  CHF₃ Pr-i Et CH₂ 2-thienyl O  69-712-8  CHF₃ Pr-i Et CH₂ 3-thienyl O  83-85 2-9  CF₃ Pr-i Et CH₂ 2-thienylO 1.5197 2-10 CF₃ Pr-i Et CH₂ 3-thienyl O 1.5208 2-11 CF₃ Bu-s Me CH₂2-thienyl O 1.5215 2-12 CF₃ Bu-s Me CH₂ 3-thienyl O 1.5229 2-13 CF₃ Bu-tMe CH₂ 2-thienyl O 1.5121 2-14 CF₃ Bu-t Me CH₂ 3-thienyl O  58-62 2-15CF₃ Pr-i Me CH(Me) 2-thienyl O 2-16 CF₃ Pr-i Me CH(Me) 3-thienyl O 2-17CF₃ Bu-t Me CH(Me) 2-thienyl O 2-18 CF₃ Bu-t Me CH(Me) 3-thienyl O 2-19CF₃ Ph Me CH₂ 2-thienyl O 139-142 2-20 CF₃ Ph Me CH₂ 3-thienyl O 142-1452-21 SMe Pr-i Me CH₂ 2-thienyl O 2-22 SMe Pr-i Me CH₂ 3-thienyl O 2-23Pr-i Pr-i Me CH₂ 2-thienyl O  79-81 2-24 Pr-i Pr-i Me CH₂ 3-thienyl O101-103 2-25 CF₃ Pr-i Me CH₂ 5-Cl-2-thienyl O  94-95 2-26 CF₃ Pr-i MeCH₂ 5-Me-2-thienyl O 2-27 SMe Pr-i Me CH₂ 5-Cl-2-thienyl O 2-28 SMe Pr-iMe CH₂ 5-Me-2-thienyl O

 

TABLE 28 m.p. (° C.) or refractive Compound index No. R¹ R² R³ Z Ar Q(n_(D) ²⁰) 2-29 Pr-i Pr-i Me CH₂ 5-Cl-2-thienyl O 2-30 Pr-i Pr-i Me CH₂5-Me-2-thienyl O 2-31 CF₃ Ph Me CH₂ 5-Cl-2-thienyl O 79-81 2-32 CF₃ PhMe CH₂ 5-Me-2-thienyl O 111-113 2-33 CF₃ Ph Me CH(Me) 2-thienyl O 2-34CF₃ Ph Me CH(Me) 3-thienyl O 2-35 CF₃ Pr-i Me CH₂ 5-CF₃-2-thienyl O 2-36CF₃ Pr-i Me CH₂ 5-F-2-thienyl O 2-37 CF₃ Pr-i Me CH₂ 3-Cl-2-thienyl O2-38 CF₃ Pr-i Me CH₂ 3-F-2-thienyl O 2-39 CF₃ Pr-i Me CH₂ 5-Cl-3-thienylO 2-40 CF₃ Pr-i Me CH₂ 5-Me-3-thienyl O 2-41 CF₃ Pr-i Me CH₂4-Br-pyrazol-1-yl O 160-161 2-42 CF₃ Bu-t Me CH₂ 5-Cl-2-thienyl O106-107 2-43 CF₃ Pr-i Me CH₂O 5-Cl-2-pyridyl O 145-147 2-44 CF₃ Pr-i MeCH₂O 5-Cl-3-pyridyl O 120-122 2-45 CF₃ Pr-i Me CH₂O3-Cl-5-CF₃-pyridin-2-yl O 138-141 2-46 CF₃ Pr-i Me CH₂O1-Me-3-CF₃5-Pyrazolyl O 108-112 2-47 CF₃ Pr-i Me CH₂O5-CF₃-1,3,4-thiaziazol-2-yl O 121-122 2-48 CF₃ Pr-i Me CH₂O2-benzothiazolyl O 192-195 2-49 CF₃ Pr-i Me CH₂O 4-CF₃-pyridin-2-yl O164-167 2-50 CF₃ Pr-i Me CH₂ 5-Me-2-thienyl O 73-75 2-51 CF₃ Bu-i Me CH₂2-thienyl O 68-70 2-52 CF₃ Bu-i Me CH₂ 3-thienyl O 81-82 2-53 CF₃ Bu-iMe CH₂ 5-Me-2-thienyl O 94-98 2-54 CF₃ Pr-i Me CH₂ Pr-e O 86-87 2-55 CF₃

Me CH₂ 2-thienyl O 92-93 2-56 CF₃

Me CH₂ 3-thienyl O 111-112 2-57 CF₃ Bu-s Me CH₂ 5-Cl-2-thienyl O 1.5295

 

TABLE 29 m. p. (° C.) or refractive Compound index No. R¹ R² R³ Z Ar Q(n_(D) ²⁰) 2-58 CF₃

Me CH₂ 5-Cl-2-thienyl O Not Measurable 2-59 CF₃

Me CH₂ 5-Me-2-thienyl O  71-74 2-60 CF₃ Pr-i Me CH(Me) 5-Me-2-thienyl O1.5141 2-61 CF₃ Pr-i Me CH(Me) 5-Br-2-thienyl O 1.5331 2-62 CF₃ Pr-i MeCH(Me) 2-thienyl O Not more than 30° C. 2-63 CF₃ Pr-i Me N(Me) 3-thienylO 1.5244 2-64 CF₃ Pr-i Me NH 2-benzothiazolyl O 180-182 2-65 CF₃ Pr-i MeN(Me) 5-Cl-pyridin-2-yl O  39-40 2-66 CF₃ Pr-i Me NH cycrohexyl O110-112 2-67 CF₃ Pr-i Me N(Me) 3-Me-5-isoxazolyl O 1.4939 2-68 CF₃ Pr-iMe N(Me) 4-MeO-6-Me-pyrimidin-2-yl O 107-110 2-69 CF₃ Pr-i Me N(Me)4,6-(MeO)₂-1,3,5-triazinyl O 112-113 2-70 CF₃ Pr-i Me N(Me)6-MeO-pyridin-3-yl O 1.5079 2-71 Pr-i Pr-i Me CH₂ 5-Cl-2-thienyl O112-115 2-72 CF₃ Pr-i Me N(Me) cycrohexyl O  98-100 2-73 Et Pr-i CH₂C≡CHCH₂ 5-Cl-2-thienyl O  90-91 2-74 CF₃ Pr-i CH₂C≡CH CH₂ 5-Cl-2-thienyl O117-118 2-75 Et Pr-i Me CH₂ 5-Cl-2-thienyl O Not Measurable 2-76 Pr-iCH₂OMe Me CH₂ 5-Cl-2-thienyl O 1.5488 2-77 CH₂OMe Pr-i Me CH₂5-Cl-2-thienyl O 1.5508 2-78 CF₃ Pr-i CH₂C≡CH CH₂ 3-thienyl O 112-1142-79 Pr-i Pr-i CH₂C≡CH CH₂ 3-thienyl O 128-131 2-80 CF₂Cl Pr-i Me O1-naphtyl O 123-126 2-81 CF₃ Pr-i Me CH₂ 5-CF₃-1,3,4-thiadizol-2-yl O2-82 CF₃ Pr-i Me CH₂ 4-CF₃-1,3,4-imidazol-2-yl O 2-83 CF₃ Pr-i Me CH₂2-Cl-5-oxazolyl O 2-84 CF₃ Pr-i Me CH₂ 2-Cl-5-thiazolyl O 2-85 CF₃ Pr-iMe CH₂ 5-Cl-2-furyl O

 

TABLE 30 m.p. (° C.) or refractive Compound index No. R¹ R² R³ Z Ar Q(n_(D) ²⁰) 2-86 CF₃ Pr-i Me CH₂ 2-benzoxazolyl O 2-87 Et Pr-i Me CH₂2-thienyl O 2-88 Et Pr-i Me CH₂ 3-thienyl O 2-89 Et Pr-i Me CH₂5-Me-2-thienyl O 2-90 Et Pr-i Me CH(Me) 2-thienyl O 2-91 Et Pr-i MeCH(Me) 3-thienyl O 2-92 Et Pr-i Me CH(Me) 5-Cl-2-thienyl O 2-93 Et Pr-iMe CH(Me) 5-Me-2-thienyl O 2-94 Et Pr-i CH₂C≡CH CH₂ 2-thienyl O 2-95 EtPr-i CH₂C≡CH CH₂ 3-thienyl O 2-96 Et Pr-i CH₂C≡CH CH₂ 5-Me-2-thienyl O2-97 Et Bu-s Me CH₂ 2-thienyl O 2-98 Et Bu-s Me CH₂ 3-thienyl O 2-99 EtBu-t Me CH₂ 2-thienyl O 2-100 Et Bu-t Me CH₂ 3-thienyl O 2-101 Et Bu-sCH₂C≡CH CH₂ 2-thienyl O 2-102 Et Bu-s CH₂C≡CH CH₂ 3-thienyl O 2-103 EtBu-t CH₂C≡CH CH₂ 2-thienyl O 2-104 Et Bu-t CH₂C≡CH CH₂ 3-thienyl O 2-105CF₃ Pr-i Me N(Me) 2-thienyl O 2-106 CF₃ Pr-i Me N(Me) 5-Cl-2-thienyl O2-107 CF₃ Pr-i Me N(Me) 5-Me-2-thienyl O 2-108 Et Pr-i Me N(Me)2-thienyl O 2-109 Et Pr-i Me N(Me) 3-thienyl O 2-110 Et Pr-i Me N(Me)5-Cl-2-thienyl O 2-111 Et Pr-i Me N(Me) 5-Me-2-thienyl O 2-112 CF₃ Pr-iMe NHCH₂ 2-thienyl O 110-112

 

TABLE 31

m. p. (° C.) or refractive Compound index No. R₁ R₂ R₃ Z Xn R₇ R₈ (n_(D)²⁰) 3-1  CF₃ Pr-i Me CH₂ H H Me  99-101 3-2  CF₃ Pr-i Me CH₂ 4-F H Me 74-75 3-3  CF₃ Pr-i Me CH₂ 4-Cl H Me  67-68 3-4  CF₃ Pr-i Me CH₂ 4-Me HMe  85-86 3-5  CF₃ Pr-i Me CH₂ H H Pr-c 144-145 3-6  CF₃ Pr-i Me CH₂ 4-FH Pr-c 131-132 3-7  CF₃ Pr-i Me CH₂ 4-Cl H Pr-c  99-100 3-8  CF₃ Pr-i MeCH₂ 4-Me H Pr-c  82-83 3-9  CF₃ Pr-i Me CH₂ H Me H 3-10 CF₃ Pr-i Me CH₂4-F Me H 3-11 CF₃ Pr-i Me CH₂ 4-Cl Me H 3-12 CF₃ Pr-i Me CH₂ 4-Me Me H3-13 Me Pr-i Me CH₂ H Me H 3-14 Me Pr-i Me CH₂ 4-F Me H 3-15 Me Pr-i MeCH₂ 4-Cl Me H 3-16 Me Pr-i Me CH₂ 4-Me Me H 3-17 Pr-i Pr-i Me CH₂ H Me H3-18 Pr-i Pr-i Me CH₂ 4-F Me H 3-19 Pr-i Pr-i Me CH₂ 4-Cl Me H 3-20 Pr-iPr-i Me CH₂ 4-Me Me H 3-21 Me Bu-t Me CH₂ H Me H 3-22 Me Bu-t Me CH₂ 4-FMe H 3-23 Me Bu-t Me CH₂ 4-Cl Me H 3-24 Me Bu-t Me CH₂ 4-Me Me H 3-25 EtEt Me CH₂ H Et H 3-26 Et Et Me CH₂ 4-F Et H

 

TABLE 32 m.p. (° C.) or refractive Compound index No. R₁ R₂ R₃ Z Xn R₇R₈ (n_(D) ²⁰) 3-27 Et Et Me CH₂ 4-Cl Et H 3-28 Et Et Me CH₂ 4-Me Et H3-29 CF₃ Pr-i Me CH₂ H H SMe 3-30 CF₃ Pr-i Me CH₂ 4-F H SMe 3-31 CF₃Pr-i Me CH₂ 4-Cl H SMe 3-32 CF₃ Pr-i Me CH₂ 4-Me H SMe 3-33 CF₃ Ph MeCH₂ H Me H 3-34 CF₃ Ph Me CH₂ 4-F Me H 3-35 CF₃ Ph Me CH₂ 4-Cl Me H 3-36CF₃ Ph Me CH₂ 4-Me Me H 3-37 CF₃ Pr-i Me CH₂ H CF₃ H 3-38 CF₃ Pr-i MeCH₂ 4-F CF₃ H 3-39 CF₃ Pr-i Me CH₂ 4-Cl CF₃ H 3-40 CF₃ Pr-i Me CH₂ 4-MeCF₃ H 3-41 OMe Pr-i Me CH₂ 4-Cl OMe H 107-109 3-42 CF₃ Pr-i Me O 4-Cl HMe 104-107 3-43 CF₃ Pr-i Me O 4-Cl H Pr-c 1.5178

 

TABLE 33

m. p. (° C.) or refractive Compound index No. R¹ R² R³ Ar (n_(D) ²⁰)4-1  CF₃ Pr-i Me Ph(4-Cl) 1.5246 4-2  Et Pr-i Me Ph 1.5446 4-3  Et Pr-iMe Ph(4-F) 1.5399 4-4  Et Pr-i Me Ph(3-F) 1.541 4-5  Et Pr-i Me Ph(2-F)1.5441 4-6  Et Pr-i Me Ph(4-Cl) 1.5562 4-7  Et Pr-i Me Ph(4-Me) 1.54754-8  Et Pr-i Me Ph(4-CN) 1.5527 4-9  Et Pr-i Me Ph(4-OMe) 102-103 4-10Et Pr-i Me Ph(4-NO₂) 106-107 4-11 Pr-i Pr-i Me Ph(4-F)  93-95 4-12CH₂OMe Pr-i Me Ph(4-F) 1.5365 4-13 CH(OEt)₂ Pr-i Me Ph(4-F) 1.5234 4-14Et Pr CH₂C≡CH Ph(4-F) 1.5445 4-15 CF₃ Pr-i Me Ph 1.518 4-16 Pr-i Pr-i MePh(4-CF₃) 4-17 CF₃ Pr-i Me Ph(4-F) 4-18 CF₃ Pr-i Me Ph(3-F) 4-19 CF₃Pr-i Me Ph(2-F) 4-20 CF₃ Pr-i Me Ph(4-Me) 4-21 CF₃ Pr-i Me Ph(4-CN) 4-22CF₃ Pr-i Me Ph(4-OMe) 4-23 CF₃ Pr-i Me Ph(4-NO₂) 4-24 CF₃ Pr-i CH₂C≡CHPh(4-F) 4-25 CF₃ Pr-i Me Ph(2-Me) 4-26 Et Pr-i Me Ph(2-Me) 1.5512 4-27CF₃ Pr-i M Ph(3-Me) 4-28 Et Pr-i Me Ph(3-Me) 1.5499

 

TABLE 34 m. p. (° C.) or refractive Compound index No. R¹ R² R³ Ar(n_(D) ²⁰) 4-29 CF₃ Pr-i CH₂C≡CH Ph(4-F) 4-30 Et Pr-i CH₂C≡CH Ph(4-Cl)4-31 CF₃ Pr-i CH₂C≡CH Ph(4-Cl) 4-32 Et Pr-i CH₂C≡CH Ph 4-33 CF₃ Pr-iCH₂C≡CH Ph 4-34 Et Pr-i CH₂C≡CH Ph(4-Me) 4-35 CF₃ Pr-i CH₂C≡CH Ph(4-Me)4-36 CF₂Cl Pr-i Me Ph 1.5382 4-37 CF₂Cl Pr-i Me Ph(4-F) 1.4929 4-38 Pr-iPr-i Me

132-133 4-39 Pr-i Pr-i Me 4-40 Pr-i Pr-i Me Ph(3-F) 4-41 Pr-i Pr-i MePh(2-F) 4-42 Pr-i Pr-i Me Ph(4-Me) 4-43 Pr-i Pr-i Me Ph(4-CN) 4-44 Pr-iPr-i Me Ph(4-OMe) 4-45 Pr-i Pr-i Me Ph(4-NO₂) 4-46 Pr-i Pr-i CH₂C≡CHPh(4-F) 4-47 Pr-i Pr-i Me Ph(2-Me) 4-48 Pr-i Pr-i Me Ph(3-Me) 4-49 Pr-iPr-i CH₂C≡CH Ph(4-F) 4-50 Pr-i Pr-i CH₂C≡CH Ph(4-Cl) 4-51 Pr-i Pr-iCH₂C≡CH Ph 4-52 Pr-i Pr-i CH₂C≡CH Ph(4-Me) 4-53 Et Pr-i Me Ph(4-CF₃)1.5117 4-54 Et Et Me Ph(4-F) 1.5462 4-55 Et Pr-i Me 2-thienyl 109-110

 

TABLE 35

m. p. (° C.) or refractive Compound index No. R¹ R² p Q q Xn (n_(D) ²⁰)5-1  CF₃ Pr-i 2 O 0 H 126-128 5-2  CF₃ Pr-i 2 O 0 4-F 1.5279 5-3  CF₃Pr-i 2 O 0 4-Cl 5-4  CF₃ Pr-i 2 O 0 4-Me 5-5  CF₃ Pr-i 3 O 0 H 5-6  CF₃Pr-i 3 O 0 4-F 5-7  CF₃ Pr-i 3 O 0 4-Cl 5-8  CF₃ Pr-i 3 O 0 4-Me 5-9 CF₃ Pr-i 2 O 1 H  93-95 5-10 CF₃ Pr-i 2 O 1 4-F 1.5090 5-11 CF₃ Pr-i 2 O1 4-Cl 5-12 CF₃ Pr-i 2 O 1 4-Me 5-13 CF₃ Pr-i 3 O 1 H 1.5181 5-14 CF₃Pr-i 3 O 1 4-F 5-15 CF₃ Pr-i 3 O 1 4-Cl 5-16 CF₃ Pr-i 3 O 1 4-Me 5-17CF₃ Pr-i 3 S 0 H 5-18 CF₃ Pr-i 3 S 0 4-F 5-19 CF₃ Pr-i 3 S 0 4-Cl 5-20CF₃ Pr-i 3 S 0 4-Me 5-21 CF₃ Pr-i 3 S 1 H 5-22 CF₃ Pr-i 3 S 1 4-F 5-23CF₃ Pr-i 3 S 1 4-Cl 5-24 CF₃ Pr-i 3 S 1 4-Me 5-25 CF₃ Pr-i 2 S 1 H138-140

 

TABLE 36 m.p. (° C.) or refractive Compound index No. R¹ R² p Q q Xn(n_(D) ²⁰) 5-26 CF₃ Pr-i 2 S 1 4-F 5-27 CF₃ Pr-i 2 S 1 4-Cl 5-28 CF₃Pr-i 2 S 1 4-Me 5-29 Et Pr-i 3 O 0 H 5-30 Et Pr-i 3 O 0 4-F 5-31 Et Pr-i3 O 0 4-Cl 5-32 Et Pr-i 3 O 0 4-Me 5-33 Et Pr-i 2 O 1 H 5-34 Et Pr-i 2 O1 4-F 5-35 Et Pr-i 2 O 1 4-Cl 5-36 Et Pr-i 2 O 1 4-Me 5-37 Et Pr-i 3 O 1H 5-38 Et Pr-I 3 O 1 4-F 5-39 Et Pr-i 3 O 1 4-Cl 5-40 Et Pr-i 3 O 1 4-Me5-41 Et Pr-i 3 S 0 H 5-42 Et Pr-i 3 S 0 4-F 5-43 Et Pr-i 3 S 0 4-Cl 5-44Et Pr-i 3 S 0 4-Me 5-45 Et Pr-i 3 S 1 H 5-46 Et Pr-i 3 S 1 4-F 5-47 EtPr-i 3 S 1 4-Cl 5-48 Et Pr-i 3 S 1 4-Me

 

TABLE 37

m. p. (° C.), refractive index Compound (n_(D) ²⁰) or NMR (δ(ppm), No.R¹ R² R³ 300 MHz, CDCl₃) 6-1 Pr-i Pr-i Me 44-45 6-2 Pr-i Et Me 1.49026-3 Et Pr-i Me 0.86(3H, d); 0.99(3H, d); 1.32(3H, t); 1.65(1H, br);1.85-1.95(1H, m); 2.23(3H, s); 2.77-2.95(2H, m); 3.58(1H, d); 8.68(1H,s); 9.02(1H, s) 6-4 Pr Pr-i Me 0.86(3H, d); 0.99(3H, d); 1.00(3H, t);1.44(1H, br); 1.73-1.83(2H, m); 1.83-1.95(1H, m); 2.23(3H, s);2.68-2.90(2H, m); 3.59(1H, d); 8.69(1H, s); 9.01(1H, s) 6-5 Pr-i Pr Me1.4929 6-6 Et Bu-t Me 74-75 6-7 Bu-t Et Me 1.02(3H, t); 1.46(9H, s);1.65-1.72(1H, m); 2.33(3H, s); 4.16(1H, t); 8.85(1H, s); 9.00(1H, s) 6-8Pr-i CH(OEt)₂ Me 1.4794 6-9 CH(OEt)₂ Pr-i Me 0.85(3H, d); 0.99(3H, d);1.24(3H, t); 1.45(1H, br); 1.95-2.04(1H, m); 2.23(1H, s); 3.53-3.66(2H,m); 3.72-4.04(2H, m); 4.03(1H, d); 5.57(1H, s); 8.87(1H, s); 9.09(1H, s)

 

TABLE 38 Compound m.p. (° C.), refractive index (n_(D) ²⁰ ) or No. R¹ R²R³ NMR (δ (ppm), 300 MHz, CDCl₃) 6-10 CH(OEt)₂ Pr-n Me 1.4811 6-11CH(OEt)₂ Bu-t Me 1.4781 6-12 Pr Pr Me 1.4978 6-13 Et Pr Me 6-14 Pr Et Me6-15 Pr-i CH₂OMe Me 1.29(3H, d), 1.29(3H, d), 2.29(3H, s), 3.39(3H, s),3.30-3.46(2H, m), 3.30- 3.46(1H, m), 4.1(1H, dd), 8.80(1H, s), 9.07(1H,s) 6-16 CH₂OMe Pr-i Me 0.83(3H, d); 1.01(3H, d); 1.89- 2.63(1H, m);2.22(3H, s); 3.46(3H, s); 3.61(1H, d); 4.64(2H, q); 8.80(1H, s);9.10)1H, s) 6-17 SMe Pr-i Me 1.5509 6-18 Pr-i Pr-i CH₂C≡CH 0.86(3H, d);1.01(3H, d); 1.88- 1.95(1H, m); 2.22(1H, t); 2.95(1H, dd); 3.38-3.48(1H,m); 3.38-3.44(1H, dd); 4.04(1H, d); 8.71(1H, s); 9.06(1H, s) 6-19 Pr-iEt CH₂C≡CH 6-20 Et Pr-i CH₂C≡CH 1.5185 6-21 Pr Pr-i CH₂C≡CH 46-48 6-22Pr-i Pr CH₂C≡CH 0.86(3H, d); 0.93(3H, d); 1.29(3H, d); 1.29(3H, d);1.27-1.42(2H, m); 1.55- 1.70(2H, m): 2.23(1H, t); 3.03(1H, dd);3.40(1Hdd); 3.37-3.50(1H, m); 4.29(1H, t); 8.74(1H, s); 9.05(1H, s) 6-23Et Bu-t CH₂C═CH 0,95(9H, s); 1.33(3H, t); 2.22(1H, t); 2.88(1F, dd);2.93(2H, q); 3.41(1H, dd); 4.11(1H, s); 8.79(1H, s); 9.02(1H, s)

 

TABLE 39 m. p. (° C.), refractive index Compound (n_(D) ²⁰) or NMR(δ(ppm), No. R¹ R² R³ 300 MHz, CDCl₃) 6-24 Bu-t Et CH₂C≡CH 6-25 Pr PrCH₂C≡CH 6-26 Et Pr CH₂C≡CH 0.87(3H, t); 0.94(3H, t); 1.18-1.45(2H, m);1.33(3H, t); 1.55-1.74(2H, m); 2.45(1H, t); 2.87(2H, q); 3.04(1H, dd);3.43(1H, dd); 4.25(1H, t); 8.75(1H, s); 9.01(1H, s) 6-27 Pr Et CH₂C≡CH6-28 Et CH(Me)(SMe) N(Me) 0.89(3H, t); 0.94(3H, t); 1.47(1H, br);1.66(3H, d); 1.68(3H, d); 1.60-1.81(2H, m); 2.05(3H, s); 2.07(3H, s);2.29(3H, s); 2.33(3H, s); 3.77(1H, t); 3.86(1H, t); 4.33(1H, q);4.42(1H, q); 8.71(1H, s); 8.77(1H, s); 9.08(1H, s) 6-29 Ph Pr-i N(Me)1.5632 6-30 Pr-i Me N(Me) 1.5012 6-31 Bu-t Me N(Me) 72-73 6-32 Pr-i PhN(Me) 1.5598 6-33 CMe(OMe)₂ Pr-i N(Me) 75-76 6-34 Pr-i

N(Me) 79-78 6-35 Pr-i CH═NOMe N(Me) 1.5079 6-36

Pr-i N(Me) 1.5089 6-37 Et Et N(Me) 1.5049

 

The compound of the present invention can be produced, for example, bythe following processes, but is not restricted to such processes.Further, syntheses of intermediates will also be described.

In the formulae, R¹, R², R⁷ and R⁸ have the same meanings as definedabove, respectively, and R¹³ is a C₁-C₆ alkyl group.

Namely, in step (1-1), 1 equivalent of a compound represented by theformula [II-1] is reacted with from 1 to 10 equivalents of a compoundrepresented by the formula [II-2] in acetic anhydride to obtain acompound represented by the formula [II-4]. Here, from 0.01 to 1.0equivalent of a catalyst (such as zinc chloride) may be added, as thecase requires.

The reaction is carried out in a nitrogen stream, as the case requires.The reaction is carried out at an optional temperature from roomtemperature to the reflux temperature in the reaction system and will becompleted in from 1 to 100 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (1-2), 1 equivalent of a compound represented by theformula [II-4] is reacted with from 1 to 10 equivalents of a Lewis acidsalt of a compound represented by the formula [II-6] in the presence offrom 1 to 10 equivalents of a base in an inert solvent to obtain acompound represented by the formula [II-7]. By this reaction, in somecases, a compound represented by the formula [II-8] will also beobtained as a by-product.

Here, the inert solvent may, for example, be an ether such as diethylether, tetrahydrofuran or dioxane, or a hydrocarbon such as n-hexane,benzene, toluene or xylene.

The base may, for example, be an alkali metal such as sodium orpotassium, an alkali metal alkoxide such as sodium methoxide orpotassium tert-butoxide, or an alkali metal hydride such as sodiumhydride or potassium hydride.

The Lewis acid may, for example, be acetic acid or hydrochloric acid.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 hour to 24 hours, although it varies depending uponthe compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

Further, in step (1-3), 1 equivalent of a compound represented by theformula [II-1] is reacted with from 1 to 10 equivalents of a compoundrepresented by the formula [II-3] in an inert solvent or without usingany to solvent, to obtain a compound represented by the formula [II-5].

Here, the inert solvent may, for example, be a hydrocarbon such asn-hexane, benzene, toluene or xylene.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 24 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

Further, in step (1-4), 1 equivalent of a compound represented by theformula [II-5] is reacted with from 1 to 5 equivalents of a Lewis acidsalt of a compound represented by the formula [II-6] in an inert solventin the presence of from 1 to 10 equivalents of a base to obtain acompound represented by the formula [II-7]. In this reaction, sometimes,a compound represented by the formula [II-8] will also be obtained as aby-product.

The inert solvent may, for example, be an ether such as diethyl ether,tetrahydrofuran or dioxane, or a hydrocarbon such as n-hexane, benzene,toluene or xylene.

The base may, for example, be an alkali metal such as sodium orpotassium, an alkali metal alkoxide such as sodium methoxide orpotassium tert-butoxide, or an alkali metal hydride such as sodiumhydride or potassium hydride.

The Lewis acid may, for example, be acetic acid or hydrochloric acid.

The reaction may be carried out in a nitrogen tag stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

L¹ represents a halogen atom, and R¹, R², R⁷ and R⁸ in the formulae,have the same meanings as defined above, respectively.

Namely, in step (2-1), 1 equivalent of a compound represented by theformula [II-7] is reduced with from 0.5 to 10 equivalents of a reducingagent (such as a borane-tert-butylamine complex or sodium borohydride)in an inert solvent to obtain a compound represented by the formula[III-3].

The inert solvent may, for example, be an alcohol such as ethyl alcohol,isopropyl alcohol, tert-butyl alcohol or methyl alcohol.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

In step (2-2), 1 equivalent of a compound represented by the formula[III-1] is reacted with from 1 to 10 equivalents of a compoundrepresented by the formula [III-2] in an inert solvent in the presenceof from 1 to 10 equivalents of magnesium, or an alkyl lithium such asmethyl lithium, ethyl lithium or n-butylithium, to obtain a compoundrepresented by the formula [III-3].

Here, the inert solvent may, for example, be an ether such as diethylether, tetrahydrofuran or dioxane, or a hydrocarbon such as n-hexane,benzene, toluene or xylene.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−100° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

Further, the compound represented by the formula [III-1] as theintermediate to be used in the above production process, can besynthesized, for example, by a method disclosed in e.g. thespecification of international application WO97/37978.

In step (2-3), 1 equivalent of a compound represented by the formula[III-4] is reacted with from 1 to 10 equivalents of a compoundrepresented by the formula [III-5] in an inert solvent in the presenceof from 1 to 10 equivalents of magnesium or an alkyl lithium such asmethyl lithium, ethyl lithium or n-butylithium, to obtain a compoundrepresented by the formula [III-3].

Here, the inert solvent may, for example, be an ether such as diethylether, tetrahydrofuran or dioxane, or a hydrocarbon such as n-hexane,benzene, toluene or xylene.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−100° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

In the formulae, L² represents a C₁-C₆ alkyl group or a phenyl groupwhich may be substituted by a C₁-C₆ alkyl group, and R¹, R², R³, R⁷, R⁸and L¹ have the same meanings as defined above, respectively.

Namely, in step (3-1), 1 equivalent of a compound represented by theformula [III-3] is chlorinated with from 1 to 10 equivalents of achlorinating agent (such as thionyl chloride or hydrogen chloride) in aninert solvent, to obtain a compound represented by the formula [IV-1].

Here, the inert solvent may, for example, be a halogenated hydrocarbonsuch as chloroform or dichloromethane, an ether such as diethyl ether,tetrahydrofuran or dioxane, or a hydrocarbon such as n-hexane, benzene,toluene or xylene.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

In step (3-2), 1 equivalent of a compound represented by the formula[IV-1] is reacted with from 1 to 10 equivalents of a compoundrepresented by the formula [IV-3] in an inert solvent, to obtain acompound represented by the formula [IV-4].

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, an ether such as diethylether, tetrahydrofuran or dioxane, a hydrocarbon such as n-hexane,benzene, toluene or xylene, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

Further, in step (3-3), 1 equivalent of a compound represented by theformula [III-3] is reacted with from 1 to 10 equivalents of a compoundrepresented by the formula [IV-8] in an inert solvent in the presence orabsence of from 1 to 10 equivalents of a base, to obtain a compoundrepresented by the formula [IV-2].

Here, the inert solvent may, for example, be a halogenated hydrocarbonsuch as chloroform or dichloromethane, an ether such as diethyl ether,tetrahydrofuran or dioxane, a hydrocarbon such as n-hexane, benzene,toluene or xylene, or a pyridine such as pyridine.

The base may, for example, be sodium hydride, pyridine, triethylamine,1,8-diazabicyclo[5.4.03]-7-undecene, sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, sodium methoxide or potassium tert-butoxide.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

Further, in step (3-4), 1 equivalent of a compound represented by theformula [IV-2] is reacted with from 2 to 10 equivalents of a compoundrepresented by the formula [IV-3] in an inert solvent, to obtain acompound represented by the formula [IV-4].

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, an ether such as diethylether, tetrahydrofuran or dioxane, a hydrocarbon such as n-hexane,benzene, toluene or xylene, a pyridine'such as pyridine, or water.

The reaction may be carried in a nitrogen stream, as the case requires.The reaction is carried out at an optional temperature from −10° C. tothe ref lux temperature in the reaction system and will be completed infrom 1 to 24 hours, although it varies depending upon the compound. Thedesired product can be isolated from the reaction solution by a usualmethod and may be purified by distillation or column chromatography, asthe case requires.

In step (3-5), 1 equivalent of a compound represented by the formula[III-3] is azidated with from 1 to 10 equivalents of an azidation agentsuch as tosyl azide, diphenylphospholyl azide, sodium azide, lithiumazide or hydrogen azide in the presence or absence of borontrifluoridediethylether complex, triphenyl phosphine and trifluoroaceticacid in an inert solvent, to obtain a compound represented by theformula [IV-5].

Here, the inert solvent may, for example, be a halogenated hydrocarbonsuch as chloroform or dichloromethane, an ether such as diethyl ether,tetrahydrofuran or dioxane, an aprotic polar solvent such asacetonitrile, N,N-dimethylformamide or dimethylsulfoxide, or ahydrocarbon such as n-hexane, benzene, toluene or xylene.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

In step (3-6), 1 equivalent of a compound represented by the formula[IV-5] is treated with from 1 to 10 equivalents of reducing agent suchas magnesium, lithium aluminum hydride, sodium borohydride,triphenylphosphine, or iron, or subjected to a hydrogenation catalyticreduction with a catalyst such as palladium carbon, platinum carbon orRaney Nickel, to obtain a compound represented by the formula [IV-6] inan inert solvent.

Here, the inert solvent may, for example, be a halogenated hydrocarbonsuch as chloroform or dichloromethane, an ether such as diethyl ether,tetrahydrofuran or dioxane, an alcohol such as methyl alcohol or ethylalcohol, or a hydrocarbon such as n-hexane, benzene, toluene or xylene.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

In step (3-7), 1 equivalent of a compound represented by the formula[IV-6] is reacted with from 1 to 10 equivalents of a compoundrepresented by the formula [IV-7] in an inert solvent in the presence orabsence of from 1 to 10 equivalents of a base, to obtain a compoundrepresented by the formula [IV-4].

Here, the inert solvent may, for example, be a halogenatedhydrocarbonsuch as chloroform or dichloromethane, an ether such as diethyl ether,tetrahydrofuran or dioxane, an alcohol such as methyl alcohol or ethylalcohol, a hydrocarbon such as n-hexane, benzene, toluene or xylene, anaprotic polar solvent such as acetonitrile, N,N-dimethylformamide ordimethylsulfoxide, a pyridine such as pyridine, or water.

The base may, for example, be sodium hydride, pyridine, triethylamine,1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, sodium methoxide or potassium tert-butoxide.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

In the formulae, R¹, R², R³, R⁷, R⁸, Z and Ar have the same meanings asdefined above, respectively.

Namely, in step (4-1), 1 equivalent of a compound represented by theformula [IV-4] is reacted with from 1 to 10 equivalents of a compoundrepresented by the formula [V-1] in an inert solvent in the presence orabsence of from 1 to 10 equivalents of a base, or 1 equivalent of acompound represented by the formula [IV-4] is reacted with from 1 to 10equivalents of a compound represented by the formula [V-2] in an inertsolvent in the presence of from 1 to 10 equivalents of a condensingagent (such as 1-ethyl-3-(3-dimethylaminopropyl)carbodiimidehydrochloride or 1,1′-carbonylbis-1H-imidazole), to obtain the desiredcompound of the present invention represented by the formula [V].

Here, the inert solvent may, for example, be a halogenated hydrocarbonsuch as chloroform or dichloromethane, an ether such as diethyl ether,diisopropyl ether, tetrahydrofuran or dioxane, a hydrocarbon such asn-hexane, benzene, toluene or xylene, or an aprotic polar solvent suchas acetonitrile, N,N-dimethylformamide or dimethylsulfoxide.

The base may, for example,be an inorganic base such as potassiumcarbonate, sodium carbonate, potassium hydrogencarbonate, sodiumhydrogencarbonate, sodium hydroxide or potassium hydroxide, or anorganic base such as pyridine or triethylamine.

Each reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 100 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

In the formulae, R¹, R², R³, R⁷, R⁸, Z and Ar have the same meanings asdefined above, respectively.

Namely, in step (5-1), 1 equivalent of the compound of the presentinvention represented by the formula [V] is reacted with from 0.3 to 10equivalents of diphosphorus pentasulfide or a Lawson reagent in an inertsolvent, to obtain the desired compound of the present inventionrepresented by the formula [VI].

Here, the inert solvent may, for example, be a hydrocarbon such asn-hexane, benzene, toluene or xylene, or a pyridine such as pyridine.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 100 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

In the formulae, R¹, R², R³, R⁴, R⁵, R⁶, R^(6a) R⁷, R⁸, Ar and L¹ havethe same meanings as defined above, respectively.

Namely, in step (6-1), 1 equivalent of a compound of the formula [IV-4]is reacted with from 0.5 to 5 equivalents of a compound represented bythe formula [VII-1] or a compound represented by the formula [VII-2] inan inert solvent in the presence or absence of from 1 to 10 equivalentsof a base, to obtain the desired compound of the present inventionrepresented by the formula [VII-3].

The base may, for example, be sodium hydride, pyridine, triethylamine,1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, sodium methoxide or potassium tert-butoxide

Here, the inert solvent may, for example, be a halogenated hydrocarbonsuch as chloroform or dichloromethane, an ether such as diethyl ether,tetrahydrofuran or dioxane, an alcohol such as methyl alcohol, isopropylalcohol or ethyl alcohol, a hydrocarbon such as n-hexane, benzene,toluene or xylene, an aprotic polar solvent such as acetonitrile,N,N-dimethylformamide or dimethylsulfoxide, a pyridine such as pyridine,or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (6-2), 1 equivalent of the compound of the presentinvention represented by the formula [VII-3] is reacted with from 1 to10 equivalents of a compound represented by the formula [VII-4] in aninert solvent in the presence or absence of from 1 to 10 equivalents ofa base, to obtain the desired product of the present to inventionrepresented by the formula [VII].

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, an ether such as diethylether, tetrahydrofuran or dioxane, an aprotic polar solvent such asacetonitrile, N,N-dimethylformamide or dimethylsulfoxide, a hydrocarbonsuch as n-hexane, benzene, toluene or xylene, or water.

The base may, for example, be sodium hydride, pyridine, triethylamine,1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, sodium methoxide or potassium tert-butoxide.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

In step (6-3), 1 equivalent of a compound represented by the formula[IV-4] is reacted with from 1 to 10 equivalents of a compoundrepresented by the formula [VII-5] in an inert solvent in the presenceor absence of from 1 to 10 equivalents of a base, to obtain a compoundrepresented by the formula [VII-6].

The base may, for example, be sodium hydride, pyridine, triethylamine,1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, sodium methoxide or potassium tert-butoxide.

Here, the inert solvent may, for example, be a halogenated hydrocarbonsuch as chloroform or dichloromethane, an ether such as diethyl ether,tetrahydrofuran or dioxane, an alcohol such as methyl alcohol or ethylalcohol, a hydrocarbon such as n-hexane, benzene, toluene or xylene, anaprotic polar solvent such as acetonitrile, N,N-dimethylformamide ordimethylsulfoxide, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (6-4), step (6-5) and step (6-6), 1 equivalent of acompound represented by the formula [VII-6] is reacted with from 1 to 10equivalents of a compound represented by the formula [VII-7], a compoundrepresented by the formula [VII-8] and a compound represented by theformula [VII-9] in an inert solvent in the presence or absence of from 1to 10 equivalents of a base, to obtain the compound of the presentinvention represented by the formula [VII], a compound represented bythe formula [VII′] and a compound represented by the formula [VII″].

The base may, for example, be sodium hydride, pyridine, triethylamine,1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, sodium methoxide or potassium tert-butoxide.

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, an ether such as diethylether, tetrahydrofuran or dioxane, an aprotic polar solvent such asacetonitrile, N,N-dimethylformamide or dimethylsulfoxide, a hydrocarbonsuch as n-hexane, benzene, toluene or xylene, a pyridine such aspyridine, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

In the formulae, R¹, R², R⁷, R⁸, Z and Ar have the same meanings asdefined above, respectively, and R^(13a) is a C₁-C₆ alkyl group.

Namely, in step (7-1), 1 equivalent of a compound represented by theformula [VIII-1] is reacted with from 1 to 10 equivalents ofparaformaldehyde in an inert solvent (depending upon the conditions,using a Dean Stark or adding a catalyst), to obtain a compoundrepresented by the formula [VIII-2].

Here, the inert solvent may, for example, be a hydrocarbon such asn-hexane, benzene, toluene or xylene.

The catalyst may, for example, be an organic base such as triethylamine.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (7-2), 1 equivalent of the compound represented by theformula [VIII-2] is reacted with from 1 to 10 equivalents of a compoundrepresented by the formula [V-1] in an inert solvent, to obtain acompound represented by the formula [VIII-3].

Here, the inert solvent may, for example, be a hydrocarbon such asn-hexane, benzene, toluene or xylene.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 100 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

Further, in step (7-3), 1 equivalent of the compound of the formula[VIII-3] is reacted with from 1 to 4 equivalents of a compoundrepresented by the formula [VIII-4] in an inert solvent in the presenceor absence of from 1 to 10 equivalents of a base, to obtain the compoundof the present invention, represented by the formula [VIII].

Here, the inert solvent may, for example, be a hydrocarbon such asn-hexane, benzene, toluene or xylene.

The base may, for example, be an inorganic base such as potassiumcarbonate, sodium carbonate, potassium hydrogencarbonate, sodiumhydrogencarbonate, sodium hydroxide or potassium hydroxide, or anorganic base such as pyridine or triethylamine.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 100 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

In the formulae, R¹, R², R³, R⁷, R⁸ and Ar have the same meanings asdefined above, respectively.

Namely, in step (8-1), 1 equivalent of a compound represented by theformula [IV-4] is reacted with from 1 to 10 equivalents of a compoundrepresented by the formula [IX-1] in an inert solvent in the presence orabsence of from 1 to 10 equivalents of a base, to obtain the desiredcompound of the present invention represented by the formula [IX].

The base may, for example, be an inorganic base such as potassiumcarbonate, sodium carbonate, potassium hydrogencarbonate, sodiumhydrogencarbonate, sodium hydroxide or potassium hydroxide, or anorganic base such as pyridine or triethylamine.

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, an ether such as diethylether, tetrahydrofuran or dioxane, an aprotic polar solvent such asacetonitrile, N,N-dimethylformamide or dimethylsulfoxide, a hydrocarbonsuch as n-hexane, benzene, toluene or xylene, pyridine, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

In the formulae, R¹, R⁷, R⁸ and L¹ have the same meanings as definedabove, respectively, and each of R²¹ and R²² is a hydrogen atom or aC₁-C₆ alkyl group, R²³ is a C₁-C₆ alkoxy group, a C₂-C₆ alkenyl group, aC₂-C₆ alkynyl group, a C₁-C₆ alkylthio group, a cyano group or NR⁹R¹⁰,and R⁹ and R¹⁰ have the same meanings as defined above, respectively.

Namely, in step (9-1), 1 equivalent of a compound represented by theformula [X-1] is halogenated with from 1 to 10 equivalents of achlorinating agent (such as sulfuryl chloride, N-chlorosuccinimide orchlorine) in an inert solvent, to obtain a compound represented by theformula [X-2].

Here, the inert solvent may, for example, be a halogenated hydrocarbonsuch as chloroform or dichloromethane, an ether such as diethyl ether,tetrahydrofuran or dioxane, or a hydrocarbon such as n-hexane, benzene,toluene or xylene.

The reaction may be carried out in a nitrogen atmosphere, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (9-2), 1 equivalent of the compound represented by theformula [X-2] is reacted with from 1 to 10 equivalents of a compoundrepresented by the formula [X-3] in an inert solvent in the presence orabsence of from 1 to 10 equivalents of a base, to obtain a compoundrepresented by the formula [x-4].

The base may, for example, be sodium hydride, pyridine, triethylamine,1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, sodium methoxide or potassium tert-butoxide.

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, an ether such as diethylether, tetrahydrofuran or dioxane, a hydrocarbon such as n-hexane,benzene, toluene or xylene or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

In the formulae, R², R³, R⁷, R⁸, R⁹, R¹⁰, W, L¹ and Ar have the samemeanings as defined above, respectively, R^(13b) is a C₁-C₆ alkyl group,or a C₁-C₄ saturated carbon chain, two of which may be bonded to eachother, R^(13c) is a C₁-C₆ alkyl group, each of R¹⁴ and R¹⁵ is a hydrogenatom, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl groupor a C₃-C₆ cycloalkyl group, and s is 0 or 1.

Namely, in step (10-1), 1 equivalent of a compound represented by theformula [XI-1] is reacted with from 0.9 to 20 equivalents of an acidsuch as hydrochloric acid or sulfuric acid in an inert solvent, toobtain the desired compound of the present invention represented by theformula [XI-2].

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, a ketone such as acetoneor methyl ethyl ketone, water, or a mixed solution thereof.

The reaction may be carried out in a nitrogen stream as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (10-2), 1 equivalent of the compound of the presentinvention represented by the formula [XI-2] is reacted with from 1 to 10equivalents of hydroxylamine hydrochloride in an inert solvent in thepresence of sodium acetate, potassium acetate, sodium carbonate orpotassium carbonate, to obtain the desired compound of the presentinvention represented by the formula [XI-3].

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, an ether such as diethylether, tetrahydrofuran or dioxane, an aprotic polar solvent such asacetonitrile, N,N-dimethylformamide, or a diethylsulfoxide, ahydrocarbon such as n-hexane, benzene, toluene or xylene, a pyridinesuch as pyridine, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (10-3), 1 equivalent of a compound represented by theformula [XI-3] is reacted with from 1 to 10 equivalents of a dehydratingagent in an inert solvent, to obtain the compound of the presentinvention represented by the formula [XI-4).

The dehydrating agent may, for example, be1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride,1,1′-carbonyldiimidazole, thionyl chloride, phosphorus pentachloride,methanesulfonyl chloride, diphosgene, p-toluene sulfonyl chloride, oracetic anhydride.

Here, the inert solvent may, for example, be a halogenated hydrocarbonsuch as dichloromethane, chloroform or carbon tetrachloride, an alcoholsuch as ethyl alcohol, isopropyl alcohol or methyl alcohol, an ethersuch as diethyl ether, tetrahydrofuran or dioxane, an aprotic polarsolvent such as acetonitrile, N,N-dimethylformamide ordimethylsulfoxide, a hydrocarbon such as n-hexane, benzene, toluene orxylene, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (10-4), 1 equivalent of the compound of the presentinvention represented by the formula [XI-4] is reacted with from 1 to 10equivalents of a compound represented by the formula [XI-5] and with offrom 1 to 10 equivalents of an alkyl lithium such as methyl lithium,ethyl lithium or n-butylithium, or magnesium in an inert solvent, toobtain a compound represented by the formula [XI-6].

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

Here, the inert solvent may, for example be an ether such as diethylether, tetrahydrofuran or dioxane, a hydrocarbon such as n-hexane,benzene, toluene or xylene, or water.

Further, in step (10-5), 1 equivalent of the compound of the presentinvention represented by the formula [XI-9] is reacted with from 0.9 to20 equivalents of an acid such as hydrochloric acid or sulfuric acid inan inert solvent, to obtain the desired compound of the presentinvention represented by the formula [XI-6].

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, a ketone such as acetoneor methyl ethyl ketone, water, or a mixed solution thereof.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (10-6), 1 equivalent of the compound of the presentinvention represented by the formula [XI-6] is reacted with from 1 to 10equivalents of a compound represented by the formula [XI-7] in an inertsolvent in the presence of 1 to 10 equivalents of sodium acetate,potassium acetate, sodium carbonate or potassium carbonate, to obtainthe desired compound of the present invention represented by the formula[XI-8].

Here, the inert solvent may, for example be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, an ether such as diethylether, tetrahydrofuran or dioxane, an aprotic polar solvent such asacetonitrile, N,N-dimethylformamide or dimethylsulfoxide, a hydrocarbonsuch as n-hexane, benzene, toluene or xylene, a pyridine such aspyridine, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (10-7), 1 equivalent of the compound of the presentinvention represented by the formula [XI-2] is reacted with from 1 to 10equivalents of an oxidizing agent such as potassium permanganate,peracetic acid, hydrogen peroxide, m-chloroperbenzoic acid or sodiumhypochlorite in an inert solvent in the presence or absence of from 1 to10 equivalents of a base such as sodium hydroxide or potassiumhydroxide, to obtain the desired compound of the present inventionrepresented by the formula [XI-10].

Here, the inert solvent may, for example, be a ketone such as acetone ormethyl ethyl ketone, an alcohol such as ethyl alcohol, isopropyl alcoholor methyl alcohol, an ether such as diethyl ether, tetrahydrofuran ordioxane, water or a mixed solution thereof.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (10-8), 1 equivalent of the compound of the presentinvention represented by the formula [XI-10] is reacted with from 1 to50 equivalents of a compound represented by the formula [XI-11] in aninert solvent or without using any solvent in the presence of e.g.sulfuric acid or p-toluene sulfonic acid, to obtain the desired compoundof the present invention represented by the formula [XI-12].

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, an ether such as diethylether, tetrahydrofuran or dioxane, an aprotic polar solvent such asacetonitrile, N,N-dimethylformamide or dimethylsulfoxide, or ahydrocarbon such as n-hexane, benzene, toluene or xylene.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

In step (10-9), 1 equivalent of the compound of the present inventionrepresented by the formula [XI-10] is reacted with from 1 to 10equivalents of a chlorinating agent such as thionyl chloride in an inertsolvent, to obtain a compound represented by the formula [XI-13].

Here, the inert solvent may, for example, be a halogenated hydrocarbonsuch as dichloromethane, chloroform or carbon tetrachloride, an ethersuch as diethyl ether, tetrahydrofuran or dioxane, or a hydrocarbon suchas n-hexane, benzene, toluene or xylene.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (10-10), 1 equivalent of the compound represented by theformula [XI-13] is reacted with from 1 to 3 equivalents of a compoundrepresented by the formula [XI-11] in an inert solvent in the presenceor absence of from 1 to 6 equivalents of a base, to obtain the desiredcompound of the present invention represented by the formula [XI-12].

The base may, for example, be sodium hydride, pyridine, triethylamine,1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, sodium methoxide or potassium tert-butoxide.

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, an ether such as diethylether, tetrahydrofuran or dioxane, an aprotic polar solvent such asacetonitrile, N,N-dimethylformamide or dimethylsulfoxide, a hydrocarbonsuch as n-hexane, benzene, toluene or xylene, a pyridine such aspyridine, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

Further, in step (10-11), 1 equivalent of the compound of the presentinvention represented by the formula [XI-10] is reacted with from 1 to 3equivalents of a compound represented by the formula [XI-15] in an inertsolvent in the presence or absence of from 1 to 6 equivalents of a baseby using a peptidizing agent such as 1,1′-carbonylbis-1H-imidazole orN,N′-dicyclohexylcarbodiimide, to obtain the desired compound of thepresent invention represented by the formula [XI-14].

The base may, for example, be sodium hydride, pyridine, triethylamine,1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, sodium methoxide or potassium tert-butoxide.

Here, the inert solvent may, for example, be a halogenated hydrocarbonsuch as dichloromethane, chloroform or carbon tetrachloride, an alcoholsuch as ethyl alcohol, isopropyl alcohol or methyl alcohol, an ethersuch as diethyl ether, tetrahydrofuran or dioxane, an aprotic polarsolvent such as acetonitrile, N,N-dimethylformamide ordimethylsulfoxide, a hydrocarbon such as n-hexane, benzene, toluene orxylene, a pyridine such as pyridine, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

In step (10-12), 1 equivalent of the compound represented by the formula[XI-13] is reacted with from 1 to 3 equivalents of a compoundrepresented by the formula [XI-15] in an inert solvent in the presenceor absence of from 1 to 10 equivalents of a base, to obtain the desiredcompound of the present invention represented by the formula [XI-14].

The base may, for example, be sodium hydride, pyridine, triethylamine,1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, sodium methoxide or potassium tert-butoxide.

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, an ether such as diethylether, tetrahydrofuran or dioxane, an aprotic polar solvent such asacetonitrile, N,N-dimethylformamide or dimethylsulfoxide, a hydrocarbonsuch as n-hexane, benzene, toluene or xylene, a pyridine such aspyridine, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature fromroom temperature to the reflux temperature in the reaction system andwill be completed in from 1 to 100 hours, although it varies dependingupon the compound. The desired product can be isolated from the reactionsolution by a usual method and may be purified by distillation or columnchromatography, as the case requires.

In the formulae, R¹, R², R⁷, R⁸, Q and Ar have the same meanings asdefined above, respectively, Ms is a methanesulfonyl group, p is 2, 3 or4, and q is 1 or 0.

Namely, in steps (11-1) and (11-2), 1 equivalent of a compoundrepresented by the formula [IV-1] or a compound represented by theformula [IV-2] is reacted with from 0.9 to 3 equivalents of a compoundrepresented by the formula [XII-1] in an inert solvent in the presenceor absence of from 1 to 10 equivalents of a base, to obtain a compoundrepresented by the formula [XII-2].

The base may, for example, be sodium hydride, pyridine, triethylamine,1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, sodium methoxide or potassium tert-butoxide.

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, an ether such as diethylether, tetrahydrofuran or dioxane, an aprotic polar solvent such asacetonitrile, N,N-dimethylformamide or dimethylsulfoxide, a hydrocarbonsuch as n-hexane, benzene, toluene or xylene, a pyridine such aspyridine, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (11-3), 1 equivalent of the compound represented by theformula [XII-2] is reacted with from 1 to 10 equivalents of phosgene orthiophosgene in an inert solvent in the presence or absence of from 1 to10 equivalents of a base, to obtain the desired compound of the presentinvention, as represented by the formula [XII].

The base may, for example, be sodium hydride, pyridine, triethylamine,1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, sodium methoxide or potassium tert-butoxide.

Here, the inert solvent may, for example, be an ether such as diethylether, tetrahydrofuran or dioxane, a halogenated hydrocarbon such asdichloromethane, chloroform or carbon tetrachloride, a hydrocarbon suchas n-hexane, benzene, toluene or xylene, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

In the formulae, R^(1a) is a hydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkoxy C₁-C₆ alkyl group,a C₃-C₆ cycloalkyl group, a phenyl group or a C₁-C₄ haloalkyl group, R¹⁶is a hydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆alkynyl group, a C₁-C₆ alkoxy C₁-C₆ alkyl group, a C₃-C₆ cycloalkylgroup or a phenyl group, Y is an oxygen atom, a sulfur atom or NR⁹, R⁹has the same meaning as defined above, and r is 1 or 2.

Namely, in step (12-1), 1 equivalent of a compound represented by theformula [XIII-1] is reacted with from 1 to 10 equivalents ofN-methylformanilide or N,N-dimethylformamide and from 1 to 20equivalents of phosphorusoxychloride in an inert solvent or withoutusing any solvent, to obtain a compound represented by the formula[XIII-2].

Here, the inert solvent may, for example, be an ether such as diethylether, tetrahydrofuran or dioxane, a halogenated hydrocarbon such asdichloromethane, chloroform, carbon tetrachloride, chlorobenzene ordichlorobenzene, a hydrocarbon such as n-hexane, benzene, toluene orxylene, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−10° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it depends upon the compound.The desired product can be isolated from the reaction solution by ausual method and may be purified by distillation or columnchromatography, as the case requires.

Then, in step (12-2), 1 equivalent of the compound represented by theformula [XIII-2] is reacted with from 1 to 3 equivalents of a compoundrepresented by the formula [XIII-3] in an inert solvent in the presenceor absence of from 1 to 10 equivalents of a base, to obtain a compoundrepresented by the formula [XIII-4].

The base may, for example, be sodium hydride, pyridine, triethylamine,1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, sodium methoxide or potassium tert-butoxide.

Here, the solvent may, for example, be an alcohol such as ethyl alcohol,isopropyl alcohol or methyl alcohol, an ether such as diethyl ether,tetrahydrofuran or dioxane, an aprotic polar solvent such asacetonitrile, N,N-dimethylformamide or dimethylsulfoxide, a hydrocarbonsuch as n-hexane, benzene, toluene or xylene, a pyridine such aspyridine, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−100C to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

Further, in step (12-3), 1 equivalent of the compound represented by theformula [XIII-2] is subjected to hydrogenation and reacted in an inertsolvent by using from 1 to 8 equivalents of manganese oxide and from0.01 to 4 equivalents of a catalyst such as palladium carbon or RaneyNickel, to obtain a compound represented by the formula [XIII-5].

Here, the inert solvent may, for example, be an alcohol such as ethylalcohol, isopropyl alcohol or methyl alcohol, an ether such as diethylether, tetrahydrofuran or dioxane, a hydrocarbon such as n-hexane,benzene, toluene or xylene, a pyridine such as pyridine or water.

The reaction is carried out at an optional temperature from −10° C. tothe reflux temperature in the reaction system and will be completed infrom 1 to 24 hours, although it varies depending upon the compound. Thedesired product can be isolated from the reaction solution by a usualmethod and may be purified by distillation or column chromatography, asthe case requires.

Then, in step (12-4), 1 equivalent of the compound represented by theformula [XIII-5] is subjected to an oxidation reaction in an inertsolvent by using from 1 to 10 equivalents of oxalyl chloride, from 1 to10 equivalents of dimethylsulfoxide and from 1 to 10 equivalents oftriethylamine or the like, to obtain a compound represented by theformula [XIII-63].

Here, the inert solvent may, for example, be a halogenated hydrocarbonsuch as dichloromethane, chloroform or carbon tetrachloride, an alcoholsuch as ethyl alcohol, isopropyl alcohol or methyl alcohol, an ethersuch as diethyl ether, tetrahydrofuran or dioxane, an aprotic polarsolvent such as acetonitrile, N,N-dimethylformamide ordimethylsulfoxide, a hydrocarbon such as n-hexane, benzene, toluene orxylene, a pyridine such as pyridine, or water.

The reaction may be carried out in a nitrogen stream, as the caserequires. The reaction is carried out at an optional temperature from−80° C. to the reflux temperature in the reaction system and will becompleted in from 1 to 24 hours, although it varies depending upon thecompound. The desired product can be isolated from the reaction solutionby a usual method and may be purified by distillation or columnchromatography, as the case requires.

Now, the processes for production, a formulation method and theapplication of the compound of the present invention will be describedin detail with reference to Examples. Further, the processes forproduction of intermediates in the synthesis of the compound of thepresent invention will also be described.

PREPARATION EXAMPLE 1 Preparation ofN-methyl-N-[2-methyl-1-(4-trifluoromethylpyrimidin-5-yl)propyl]phenylacetamide(Compound No. 1-8 of the Present Invention)

6 g (26 mmol) of4-trifluoromethyl-5-[1-(N-methylamino)-2-methylpropyl]pyrimidine and 3.6g (26 mmol) of potassium carbonate were dissolved in 150 ml ofacetonitrile, and 4 g (26 mmol) of phenylacetyl chloride was dropwiseadded, followed by stirring at room temperature for 3 hours. To thereaction solution, 200 ml of water was added, followed by extractionwith ethyl acetate. The obtained organic layer was washed with water andthen dried over anhydrous magnesium sulfate. Ethyl acetate was distilledoff under reduced pressure, and the obtained crude crystals were washedwith n-hexane to obtain 7.7 g (yield: 85%) ofN-methyl-N-[2-methyl-1-(4-trifluoromethylpyrimidin-5-yl)propyl]phenylacetamideas colorless transparent crystals (melting point: 106-109° C.).

PREPARATION EXAMPLE 2 Preparation ofN-methyl-N-[2-methyl-1-(4-trifluoromethylpyrimidin-5-yl)propyl]-2-pyridylacetamide(Compound No. 2-3 of the Present Invention)

0.3 g (1.7 mmol) of 2-pyrimidinylacetate hydrochloride and 0.18 g (1.8mmol) of triethylamine were dissolved in 30 ml of tetrahydrofuran, and0.28 g (1.7 mmol) of 1,1′-carbonylbis-1H-imidazole was added, followedby stirring at room temperature for 1 hour. Then, 0.4 g (1.7 mmol) of4-trifluoromethyl-5-[1-(N-methylamino)-2-methylpropyl]pyrimidine wasadded, followed by heating and refluxing for further 3 hours. To thereaction solution, 100 ml of water was added, followed by extractionwith ethyl acetate. The obtained organic layer was washed with water andthen dried over anhydrous magnesium sulfate. Ethyl acetate was distilledoff under reduced pressure, and the obtained crude product was purifiedby silica gel column chromatography (developing solvent/n-hexane:ethylacetate:methanol=4.5:4.5:1) to obtain 0.2 g (yield: 33%) ofN-methyl-N-[2-methyl-1-(4-trifluoromethylpyrimidin-5-yl)propyl]-2-pyridylacetamideas colorless transparent crystals (melting point: 99-100° C.).

PREPARATION EXAMPLE 3 Preparation ofN-methyl-N-[2-methyl-1-(4-trifluoromethylpyrimidin-5-yl)propyl]phenylthioacetamide(Compound No. 1-142 of the Present Invention)

0.45 g (1.3 mmol) ofN-methyl-N-[2-methyl-1-(4-trifluoromethylpyrimidin-5-yl)propyl]phenylthioacetamideand 0.52 g (1.3 mmol) of a Lawson reagent were dissolved in 30 ml oftoluene, followed by heating and refluxing for 30 hours. To the reactionsolution, 100 ml of water was added, followed by extraction with ethylacetate. The obtained organic layer was washed with water and then driedwith anhydrous magnesium sulfate. Ethyl acetate m was distilled offunder reduced pressure, and the obtained crude product was purified bysilica gel column chromatography (developing solvent/n-hexane:ethylacetate=3:1) to obtain 0.12 g (yield: 26%) ofN-methyl-N-[2-methyl-1-(4-trifluoromethylpyrimidin-5-yl)propyl]phenylthioacetamideas slightly yellow crystals (melting point: 93-94° C.).

PREPARATION EXAMPLE 4 Preparation ofN-methoxymethyl-N-[2-methyl-1-(4-trifluoromethylpyrimidin-5-yl)propyl]-4-chlorophenylacetamide(Compound No. 1-105 of the Present Invention)

1.0 g (4.6 mmol) of4-trifluoromethyl-5-[1-amino-2-methylpropyl]pyrimidine, 0.23 g (6.9mmol)of paraformaldehyde and 0.1 g (9.9 mmol) of triethylamine weredissolved in 50 ml of toluene. Heating and refluxing were carried outfor 1 hour while removing water from the reaction system by means ofDean's Stark. The reaction solution was returned to room temperature,and 0.86 g (4.6 mmol) of 4-chlorophenylacetylchloride was dropwiseadded, followed by stirring for further 2 hours. To this solution, 10 mlof a toluene solution containing 0.2 g (6.2 mmol) of methanol and 0.5 g(4.9 mmol) of triethylamine, was dropwise added, followed by stirring atroom temperature for 1 hour. To the reaction solution, 100 mg of waterwas added, followed by extraction with ethyl acetate. The obtainedorganic layer was washed with water and then dried over anhydrousmagnesium sulfate. Ethyl acetate was distilled off under reducedpressure, and the obtained crude product was purified by silica gelcolumn chromatography (developing solvent/n-hexane:ethyl acetate=3:1) toobtain 0.5 g (yield: 26%) ofN-methoxymethyl-N-[2-methyl-1-(4-trifluoromethylpyrimidin-5-yl)propyl]-4-chlorophenylacetamideas colorless transparent crystals (melting point: 142-145° C.).

PREPARATION EXAMPLE 5 Preparation ofN-methyl-N-[2-methyl-1-(4-chlorodifluoromethylpyrimidin-5-yl)propyl]-N′-(4-methylphenyl)urea(Compound No. 1-37 of the Present Invention)

0.50 g (2.1 mmol) of4-chlorodifluoromethyl-5-[1-(N-methylamino)-2-methylpropyllpyrimidineand 0.28 g (2.1 mmol) of 4-methylphenyl isocyanate were dissolved in 30ml of isopropyl ether, followed by stirring at room temperature for 1hour. Precipitated crystals were collected by filtration to obtain 0.65g (yield: 84%) ofN-methyl-N-[2-methyl-1-(4-chlorodifluoromethylpyrimidin-5-yl)propyl]-N′-(4-methylphenyl)ureaas colorless transparent crystals (melting point: 135-137° C.).

PREPARATION EXAMPLE 6 Preparation of1,3-dimethyl-1-[2-methyl-1-(4-trifluoromethyl-pyrimidin-5-yl)-propyl]-3-phenylurea(Compound No. 1-424 of the Present Invention)

0.8 g (3.4 mmol) of4-trifluoromethyl-5-[1-(N-methylamino)-2-methylpropyl]pyridine wasdissolved in 30 ml of chloroform, and 5 mg of a chloroform solution of0.45 g (3.8 mmol) of phenyl isocyanate was dropwise added, followed bystirring at room temperature for 10 hours. To the reaction solution, 50ml of water was added, followed by extraction with ethyl acetate. Theobtained organic layer was washed with water and then dried overanhydrous magnesium sulfate. Ethyl acetate was distilled off underreduced pressure, and the obtained crude crystals were washed withn-hexane to obtain 1.0 g (yield: 83%) of1-methyl-1-[2-methyl-1-(4-trifluoromethyl-pyrimidin-5-yl)-propyl]-3-phenylurea.0.5 g (1.4 mmol) of the obtained1-methyl-1-(2-methyl-1-(4-trifluoromethyl-pyrimidin-5-yl)-propyl)-3-phenylureawas dissolved in 30 mg of tetrahydrofuran, and 0.06 g (2.5 mmol) ofsodium hydride was added, followed by stirring at room temperature for0.5 hour. Then, 0.22 g (1.6 mmol) of methyl iodide was dropwise added,followed by stirring at room temperature for 4 hours. To the reactionsolution, 50 ml of water was added, followed by extraction with ethylacetate. The obtained organic layer was washed with water and then driedover anhydrous magnesium sulfate. Ethyl acetate was distilled off underreduced pressure, and the obtained crude product was purified by silicagel chromatography (developing solvent/n-hexane:ethyl acetate 9:1 to3:1) to obtain 0.28 g (yield: 53.8%) of1,3-dimethyl-1-[2-methyl-1-(4-trifluoromethyl-pyrimidin-5-yl)-propyl-3-phenylureaas colorless crystals (melting point: 104-105° C.).

PREPARATION EXAMPLE 7 Preparation ofN-[1-(4-ethyl-pyrimidin-5-yl)-2-methylpropyl]-4-fluoro-N-methyl-benzenesulfonamide(Compound No. 4-3 of the Present Invention)

0.4 g (0.2 mmol) of [1-(4-ethyl-pyrimidin-5-yl)-propyl]-methyl-amine wasdissolved in 20 ml of pyridine, and 0.43 g (0.22 mmol) ofp-fluorobenzenesulfonyl chloride was dropwise added, followed bystirring at room temperature for 10 hours. To the reaction solution, 50ml of water was added, followed by extraction with diethyl ether. Theobtained organic phase was washed twice with 30 ml of a dilute citricacid aqueous solution and then dried over anhydrous magnesium sulfate.Diethyl ether was distilled off under reduced pressure, and the obtainedcrude product was purified by silica gel chromatography (developingsolvent/n-hexane:ethyl acetate 4:1 to 1:1) to obtain 0.4 g (yield: 56%)of(N-[1-(4-ethyl-pyrimidin-5-yl)-2-methylpropyl]-4-fluoro-N-methyl-benzenesulfonamideas a colorless oil (n_(D) ²⁰=1.5399).

PREPARATION EXAMPLE 8 Preparation of1-(4-chlorobenzyl)-1,3-dimethyl-3-[2-methyl-1-(4-trifluoromethyl-pyrimidin-5-yl)-propyl]-urea(Compound No. 1-532 of the Present Invention)

0.16 g (1.0 mmol) of (4-chlorobenzyl)-methylamine was dissolved in 30 mlof pyridine, and 0.3 g (1.0 mmol) ofN-methyl-N-(2-methyl-1-(4-trifluoromethyl-pyrimidin-5-yl)-propyl]-carbamoylchloride was dropwise added, followed by stirring at room temperaturefor 10 hours. To the reaction solution, 50 ml of water was added,followed by extraction with diethyl ether. The obtained organic phasewas washed twice with 30 ml of a dilute citric acid aqueous solution,followed by drying over anhydrous magnesium sulfate. Diethyl ether wasdistilled off under reduced pressure, and the obtained crude product waspurified by silica gel chromatography (developing solvent/n-hexane:ethylacetate=8:1 to 3:1) to obtain 0.22 g (yield: 52%) of1-(4-chlorobenzyl)-1,3-dimethyl-3-[2-methyl-1-(4-trifluoromethyl-pyrimidin-5-yl)-propyl]-ureaas colorless crystals (melting point: 95-98° C.).

PREPARATION EXAMPLE 9 Preparation ofN-[1-(4-diethoxymethylpyrimidin-5-yl)-2-methylpropyl]-N-methyl-2-phenylacetamide (Compound No. 1-453 of the Present Invention)

8.3 g (0.031 mol) of[1-(4-diethoxymethylpyrimidin-5-yl)-2-methylpropyl]methylamine and 6.4 g(46 mmol) of potassium carbonate were added to 100 ml of acetonitrile,and then 5.8 g (0.038 mol) of phenylacetyl chloride was dropwise addedat room temperature and reacted for 2 hours. After completion of thereaction, the product was poured into water and extracted with ethylacetate. The organic layer was washed with an aqueous citric acidsolution, water and an aqueous sodium chloride solution in this order,dried and concentrated, and the obtained oily product was purified bysilica gel column chromatography (ethyl acetate:n-hexane=1:5 to ethylacetate), to obtain 8.4 g (yield: 70%) ofN-[1-(4-diethoxymethylpyrimidin-5-yl)-2-methylpropyl]-N-methyl-2-phenylacetamide as colorless viscous liquid (n_(D) ²=1.5253)

PREPARATION EXAMPLE 10 Preparation ofN-[1-(4-formylpyrimidin-5-yl)-2-methylpropyll-N-methyl-4-fluorophenylacetamide(Compound No. 1-523 of the Present Invention)

8.4 g (2.1 mmol) ofN-[1-(4-diethoxymethylpyrimidin-5-yl)-2-methylpropyl]-N-methy4-fluorophenylacetamidewas dissolved in 100 ml of acetone, and 13 ml of 6N hydrochloric acidwas added and reacted at room temperature for 5 hours. After completionof the reaction, the reaction solution was concentrated, and an aqueoussodium hydrogencarbonate solution was added to alkaline, followed byextraction with ethyl acetate. The organic layer was washed with anaqueous citric acid solution, water and an aqueous sodium chloridesolution, in this order, dried and concentrated, and the obtained oilyproduct was purified by silica gel column chromatography (ethylacetate:n-hexane=1:5 to ethyl acetate) to obtain 5.3 g (yield: 77%) ofN-[1-(4-formylpyrimidin-5-yl)-2-methylpropyl]-N-methyl-4-fluorophenylacetamideas colorless viscous liquid (n_(D) ²⁰=1.5466).

PREPARATION EXAMPLE 11 Preparation ofN-[1-(4-hydroxyiminomethylpyrimidin-5-yl)-2-methylpropyl]-N-methylphenylacetamide(Compound No. 1-500 of the Present Invention)

1.0 g (3.2 mmol) ofN-(1-(4-formylpyrimidin-5-yl)-2-methylpropyl]-N-methylphenylacetamidewas dissolved in 30 ml of methanol, and 0.45 g (6.5 mmol) ofhydroxylamine hydrochloride and 0.63 g (6.4 mmol) of potassium acetatewere added and reacted at room temperature for 1 hour. After completionof the reaction, the product was poured into water and extracted withethyl acetate. The organic layer was washed with an aqueous sodiumhydrogencarbonate solution, an aqueous citric acid solution, water andan aqueous sodium chloride solution, in this order, dried andconcentrated, and the obtained oily product was purified by silica gelcolumn chromatography (ethyl acetate:n-hexane=1:1 to ethyl acetate) toobtain 0.45 g (yield: 43%) ofN-[1-(4-hydroxyiminomethylpyrimidin-5-yl)-2-methylpropyl]-N-methylphenylacetamideas colorless crystals (melting point: 171-172° C.).

PREPARATION EXAMPLE 12 Preparation ofN-[1-(4-cyanopyrimidin-5-yl)-2-methylpropyl]-N-methylphenylacetamide(Compound No. 1-504 of the Present Invention)

0.25 g (0.77 mmol) ofN-[1-(4-hydroxyiminomethylpyrimidin-5-yl)-2-methylpropyl]-N-methylphenylacetamidewas dissolved in 30 ml of chloroform, and 0.16 g (0.83 mmol) of1-(3-(dimethylamino)propyl]-3-ethylcarbodilmide hydrochloride was addedand reacted at room temperature for 8 hours. After completion of thereaction, the solvent was distilled off, and water was added, followedby extraction with ethyl acetate. The organic layer was washed withwater and an aqueous sodium chloride solution in this order, dried andconcentrated, and the obtained oily product was purified by silica gelcolumn chromatography (ethyl acetate:n-hexane=1:1 to ethyl acetate) toobtain 0.19 g (yield: 88%) ofN-[1-(4-cyanopyrimidin-5-yl)-2-methylpropyl]-N-methylphenylacetamide ascolorless crystals (melting point: 80-81° C.).

PREPARATION EXAMPLE 13 Preparation of2-(4-chlorophenyl)-N-[1-(4,6-dimethoxypyrimidin-5-yl)-2-methylpropyl]-N-methylacetamide (Compound No. 3-41 of the Present Invention)

0.80 g (3.8 mmol) of1-(4,6-dimethoxypyrimidin-5-yl)-2-methylpropylamine, 0.59 g (4.2 mmol)of methyl iodide and 0.46 g (4.6 mmol) of triethylamine were added to 10ml of N,N-dimethylacetamide and reacted at 80° C. for 1 hour. Aftercompletion of the reaction, the product was poured into water andextracted with toluene. The organic layer was washed with water and anaqueous sodium chloride solution in this order, dried and concentrated,and the obtained oily product was supplied to the subsequent reactionwithout purification. 0.20 g (0.89 mmol) of this oily product and 0.22 g(1.6 mmol) of potassium carbonate were added to 20 ml of acetonitrile,and then 0.30 g (1.6 mmol) of 4-chlorophenylacetyl chloride was added atroom temperature and reacted overnight. After completion of thereaction, the product was poured into water and extracted with ethylacetate. The organic layer was washed with an aqueous citric acidsolution, water and an aqueous sodium chloride solution in this order,dried and concentrated, and the obtained oily product was purified bypreparative HPLC (ethyl acetate:n-hexane=1:1) to obtain 0.21 g (yield:15%, 2 steps) of2-(4-chlorophenyl)-N-[1(4,6-dimethoxypyrimidin-5-yl)-2-methylpropyl]-N-methylacetamide as colorless crystals (melting point: 107-109° C.).

PREPARATION EXAMPLE 14 Preparation of1-[2-methyl-1-(4-trifluoromethyl-pyrimidin-5-yl)-propyl]-3-phenylimidazolin-2-one(Compound No. 5-1 of the Present Invention)

1.05 g (4.2 mol) of5-(1-chloro-2-methylpropyl)-4-trifluoromethylpyrimidine and 0.61 (4.2mol) of N-phenylethylenediamine were added to 10 ml of isopropylalcohol, followed by stirring at room temperature for 6 hours. Aftercompletion of the reaction, the reaction solution was concentrated, thenpoured into water and extracted with ethyl acetate, and purified bysilica gel column chromatography (ethyl acetate:n-hexane=1:1 to ethylacetate) to obtain 0.38 g ofN-[2-methyl-1-(4-trifluoromethylpyrimidin-5-yl)-propyl]-N′-phenylethane-1,2-diamine.Then, 0.38 g (1 mmol) ofN-[2-methyl-1-(4-trifluoromethylpyrimidin-5-yl)-propyl]-N′-phenylethane-1,2-diamineand 0.5 g (5 mmol) of triethylamine were added to 10 ml ofdichloromethane, and a dichloromethane solution containing 0.2 g (2mmol) of phosgene was dropwise added under cooling with ice. After thedropwise addition, stirring was further continued at room temperaturefor 1 hour to terminate the reaction. After termination of the reaction,the product was poured into water, washed with an aqueous sodiumhydrogencarbonate solution, dried and concentrated, and the obtainedoily product was purified by silica gel column chromatography (ethylacetate:n-hexane=1:1 to ethyl acetate) to obtain 0.25 g (yield: 61%) of1-[2-methyl-1-(4-trifluoromethyl-pyrimidin-5-yl)-propyl]-3-phenylimidazolin-2-oneas colorless crystals (melting point: 126-128° C.).

PREPARATION EXAMPLE 15 Preparation of5-(1-{[2-(4-chlorophenyl)-propionyl]methylamino}-2-methylpropyl)-pyrimidine-4-carboxylicacid (Compound No. 1-718 of the Present Invention)

A solution comprising 1.0 g (3.2 mmol) ofN-[1-(4-formylpyrimidin-5-yl)-2-methylpropyl]-N-methylphenylacetamideand 10 ml of tetrahydrofuran, was added to a solution comprising 0.23 g(4.1 mmol) of potassium hydroxide and 10 ml of water. Then, 0.88 g (5.56mmol) of potassium permanganate was further added. Then, the mixture washeated at 80° C. for 3 hours. After completion of the reaction, sodiumsulfite was added, followed by filtration. The filtrate was acidifiedwith hydrochloric acid and then extracted with ethyl acetate, and theextract was washed with an aqueous sodium chloride solution, dried overanhydrous magnesium sulfate and concentrated to obtain a crude product.This crude product was dissolved in a mixed solution of toluene, etherand acetone, followed by extraction with an aqueous potassium hydroxidesolution. Then, extract was acidified with diluted hydrochloric acid andextracted with ethyl acetate. The extract was dried over magnesiumsulfate, concentrated and further washed with isopropyl ether to obtain0.33 g (yield: 32%) of5-(1-{[2-(4-chlorophenyl)-propionyl]methylamino}-2-methylpropyl)-pyrimidine-4-carboxylicacid (diastereomer A-isomer) as slightly blown crystals (melting point:168-170° C.).

PREPARATION EXAMPLE 16 Preparation of5-(1-{[2-(4-chlorophenyl)-propionyl]methylamino}-2-methylpropyl)-pyrimidine-4-carboxylicacid methyl ester (diastereomer A-isomer) (Compound No. 1-592 of thePresent Invention)

A few drops of concentrated sulfuric acid were added to a methanolsolution of 2.00 g (5.32 mmol) of5-(1-{[2-(4-chlorophenyl)-propionyl]methylamino}-2-methylpropyl)-pyrimidine-4-carboxylicacid, followed by heating and refluxing for 5 hours. After completion ofthe reaction, water was added, followed by extraction with ethylacetate, and the extract was washed with an aqueous sodium chloridesolution, dried over magnesium sulfate and concentrated, and theobtained oily product was purified by silica gel column chromatography(ethyl acetate:n-hexane=1:1 to ethyl acetate) to obtain 0.59 g (yield:28%) of5-(1-{[2-(4-chlorophenyl)-propionyl]methylamino}-2-methylpropyl)-pyrimidine-4-carboxylicacid methyl ester (diastereomer A-isomer) as colorless oily product.

Examples for Preparation of Intermediates

REFERENCE EXAMPLE 1 Preparation of3-ethoxymethylene-1,1,1-trifluoro-5-methyl-2,4-hexanedione

A mixture comprising 213 g (1.17 mol) of1,1,1-trifluoro-5-methyl-2,4-hexanedione, 242 g (1.64 mol) of ethylorthoformate and 166 g (1.63 mol) of acetic anhydride, was heated andrefluxed for 6 hours. The solvent was distilled off under reducedpressure to obtain 146 g (yield: 67%) of3-ethoxymethylene-1,1,1-trifluoro-5-methyl-2,4-hexanedione.

REFERENCE EXAMPLE 2 Preparation of5-isopropylcarbonyl-4-trifluoromethylpyrimidine

46 g (0.85 mol) of sodium methoxide was dissolved in 700 ml of methanol,and 76 g (0.73 mol) of formamidine acetate was added, followed bystirring at room temperature for 15 minutes. Then, 146 g (0.61 mol) of3-ethoxymethylene-1,1,1-trifluoro-5-methyl-2,4-hexanedione was addedunder cooling with ice, followed by heating and refluxing for further 2hours. The solvent was distilled off under reduced pressure, and 1,000ml of ice water was added, followed by extraction with ethyl acetate.The obtained organic layer was washed with water and then dried overanhydrous magnesium sulfate. Ethyl acetate was distilled off underreduced pressure, and the obtained crude product was purified by silicagel column chromatography (developing solvent/n-hexane:ethylacetate=6:1) to obtain 89 g (yield: 67%) of5-isopropylcarbonyl-4-trifluoromethylpyrimidine as slightly yellowliquid.

REFERENCE EXAMPLE 3 Preparation of5-(1-hydroxy-2-methylpropyl)-4-trifluoromethylpyrimidine

25 g (115 mmol) of 5-isopropylcarbonyl-4-trifluorometylpyrimidine wasdissolved in 100 ml of ethanol, and under cooling with ice, 6 g (69mmol) of a borane-tert-butylamine complex was added, followed bystirring for 2 hours. Further, 20 ml of acetone was added, followed bystirring for 0.5 hour. The solvent was distilled off under reducedpressure, and the residue was purified by silica gel columnchromatography (developing solvent/n-hexane:ethyl acetate=1:1) to obtain22 g (yield: 87%) of5-(1-hydroxy-2-methylpropyl)-4-trifluoromethylpyrimidine as slightlyyellow liquid (n_(D) ²⁰=1.4481)

REFERENCE EXAMPLE 4 Preparation of5-(1-chloro-2-methylpropyl)-4-trifluoromethylpyrimidine

22 g (100 mmol) of5-(1-hydroxy-2-methylpropyl)-4-trifluoromethylpyrimidine was dissolvedin 150 ml of chloroform, and 25 ml (342 mmol) of thionyl chloride wasadded. The reaction mixture was heated and refluxed for 2 hours. Thesolvent and thionyl chloride was distilled off under reduced pressure,and the residue was purified by silica gel column chromatography(developing solvent/n-hexane:ethyl acetate=6:1) to obtain 11.6 g (yield:49%) of 5-(1-chloro-2-methylpropyl)-4-trifluoromethylpyrimidine as brownliquid (refractive index n_(D) ²⁰: 1.4558).

REFERENCE EXAMPLE 5 Preparation of5-[1-(N-methylamino)-2-methylpropyl]-4-trifluoromethylpyrimidine

4.5 g (19 mmol) of5-(1-chloro-2-methylpropyl)-4-trifluoromethylpyrimidine was dissolved in50 ml of isopropyl alcohol, and 10 ml (161 mmol) of a 50% methylamineaqueous solution was added, followed by stirring at room temperature for8 hours. The solvent was distilled off under reduced pressure, and 100ml of water was added, followed by extraction with ethyl acetate. Theobtained organic layer was washed with water and then dried overanhydrous magnesium sulfate. Ethyl acetate was distilled off underreduced pressure to obtain 3.4 g (yield: 77%) of5-(1-(N-methylamino)-2-methylpropyl]-4-trifluoromethylpyrimidine asslightly yellow liquid (refractive index n_(D) ²⁰: 1.4529).

REFERENCE EXAMPLE 6 Preparation of4-ethoxymethylene-2,6-dimethyl-3,5-heptanedione

A mixture comprising 17.2 g (110 mmol) of 2,6-dimethyl-3,5-heptanedione,22.8 g (153 mmol) of ethyl orthoformate and 31.5 g (309 mmol) of aceticanhydride, was reacted for 2 hours at 110° C. The solvent was distilledoff under reduced pressure to obtain 11.5 g (yield: 49%) of4-ethoxymethylene-2,6-dimethyl-3,5-heptanedione.

REFERENCE EXAMPLE 7 Preparation of5-isopropylcarbonyl-4-isopropylpyrimidine

11.5 g (60 mmol) of a 28% sodium methoxide solution was dissolved in 100ml of methanol, and 5.6 g (54 mmol) of formamidine acetate was added,followed by stirring at room temperature for 15 minutes. Then, 11.5 g(54 mmol) of 4-ethoxymethylene-2,6-dimethyl-3,5-heptanedione was addedunder cooling with ice. The reaction mixture was further reacted at 50°C. for one hour. The solvent was distilled off under reduced pressure,and 200 ml of water was added, followed by extraction with ethylacetate. The obtained organic layer was washed with water and then driedover anhydrous magnesium sulfate. Ethyl acetate was distilled off underreduced pressure, and the residue was purified by silica gel columnchromatography (developing solvent/n-hexane:ethyl acetate=4:1) to obtain9.2 g (yield: 89%) of 5-isopropylcarbonyl-4-isopropylpyrimidine asslightly yellow liquid.

REFERENCE EXAMPLE 8 Preparation of5-(1-hydroxy-2-methylpropyl)-4-isopropylpyrimidine

9.2 g (48 mmol) of 5-isopropylcarbonyl-4-isopropylpyrimidine wasdissolved in 50 ml of ethanol, and under cooling with ice, 2.5 g (29mmol) of a borane-tert-butylamine complex was added, followed bystirring for 2 hours. Further, 20 ml of acetone was added, followed bystirring for 0.5 hour. The solvent was distilled off under reducedpressure, and 200 ml of water was added, followed by extraction withethyl acetate. The obtained organic layer was washed with water and thendried over anhydrous magnesium sulfate. Ethyl acetate was distilled offunder reduced pressure to obtain 8.3 g (yield: 89%) of the desiredproduct i.e. 5-(1-hydroxy-2-methylpropyl)-4-isopropylpyrimidine.

REFERENCE EXAMPLE 9 Preparation of5-(1-methylsulfonyloxy-2-methylpropyl)-4-isopropylpyrimidine

8.3 g (43 mmol) of 5-(1-hydroxy-2-methylpropyl)-4-isopropylpyrimidinewas dissolved in 10 ml of pyridine, and under cooling with ice, 9.8 g(86 mmol) of methylsulfonyl chloride was dropwise added. The reactionmixture was reacted at room temperature for 2 hours, and then, 100 ml ofice water was added, followed by extraction with ethyl acetate. Theobtained organic layer was washed with an aqueous citric acid solutionand water and then dried over anhydrous magnesium sulfate. Ethyl acetatewas distilled off under reduced pressure to obtain 10.6 g (yield: 90%)of 5-(1-methylsulfonyloxy-2-methylpropyl)-4-isopropylpyrimidine.

[¹H-NMR (300 MHz CDCl₃, TMS δ (ppm)) 0.91 (3 H, d), 1.14 (3H, d), 1.31(3H, dd), 2.1-2.2 (1H, m), 2.89 (3H, s), 3.2-3.3 (3H, m) 5.56 (1H, d),8.68 (1H, s), 9.14 (1H, s)],

REFERENCE EXAMPLE 10 Preparation of5-[1-(N-methylamino)-2-methylpropyl]-4-isopropylpyrimidine

10.6 g (39 mmol) of5-(1-methylsulfonyloxy-2-methylpropyl)-4-isopropylpyrimidine wasdissolved in 50 ml of isopropyl alcohol, and 10 ml (129 mmol) of a 40%methylamine aqueous solution was added, followed by stirring at roomtemperature for 8 hours. After completion of the reaction, the solventwas distilled off under reduced pressure, and 100 ml of water was added,followed by extraction with ethyl acetate. The obtained organic layerwas washed with water and then dried over anhydrous magnesium sulfate.Ethyl acetate was distilled off under reduced pressure, and the residuewas purified by silica gel column chromatography (developingsolvent=ethyl acetate) to obtain 2.9 g (yield: 36%) of5-[1-(N-methylamino)-2-methylpropyl]-4-isopropylpyrimidine as slightlyyellow crystals (melting point: 37-39° C.).

REFERENCE EXAMPLE 11 Preparation of5-(1-hydroxy-2-methylpropyl)-4-methylthiopyrimidine

10.6 g (52 mmol) of 5-bromo-4-methylthiopyrimidine was dissolved in 100ml of tetrahydrofuran, and at −60° C., 36 ml of a n-butylithium hexanesolution (1.6 mol/l) was dropwise added. After stirring at −60° C. for30 minutes, 4.1 g (57 mmol) of isobutylaldehyde was dropwise added andfurther reacted for 1 hour. The reaction solution was poured into waterand extracted with ethyl acetate. The obtained organic layer was washedwith water and then dried over anhydrous magnesium sulfate. Ethylacetate was distilled off under reduced pressure, and the residue waspurified by silica gel column chromatography (developingsolvent/n-hexane:ethyl acetate=3:2) to obtain 2.9 g (yield: 28%) of5-(1-hydroxy-2-methylpropyl)-4-methylthiopyrimidine as slightly yellowcrystals (melting point: 123-127° C.).

REFERENCE EXAMPLE 12 Preparation of2-bromo-1-(4-ethylpyrimidin-5-yl)-propan-1-one

49.2 g (0.30 mol) of 1-(4-ethylpyrimidin-5-yl)propan-1-one was dissolvedin 500 ml of carbon tetrachloride, and 53 g (0.30 mol) ofN-bromosuccinimide and 0.3 g of azoisobutyronitrile were added, followedby refluxing for 2 hours. After cooling, crystals were removed byfiltration, and the filtrate was concentrated and the obtained oilyproduct was purified by column chromatography (ethylacetate:n-hexane=1:4 to 1:2) to obtain 64.3 g (yield: 89%) of2-bromo-1-(4-ethylpyrimidin-5-yl)-propan-1-one as yellow liquid.

REFERENCE EXAMPLE 13 Preparation of1-(4-ethylpyrimidin-5-yl)-2-methylthio-propan-1-one

10.0 g (0.041 mol) of 2-bromo-1-(4-ethylpyrimidin-5-yl)propan-1-one wasdissolved in 40 ml of isopropyl alcohol, and 21 g (0.045 mol) of a 15%sodium methythiolate aqueous solution was added under cooling with iceand then reacted at room temperature for 1 hour. After completion of thereaction, the product was poured into water and extracted with ethylacetate. The organic layer was washed with an aqueous sodium chloridesolution, dried and concentrated to obtain 9.5 g of crude1-(4-ethylpyrimidin-5-yl)-2-methylthio-propan-1-one. The product wasused for the subsequent reaction without purification.

REFERENCE EXAMPLE 14 Preparation of4,6-dichloropyrimidine-5-carboaldehyde

To 65.0 g (0.89 mol) of N,N-dimethylformamide, 356 g (2.3 mol) ofphosphorus oxychloride was added at a temperature of at most 20° C.under cooling with ice, followed by stirring at room temperature for 10minutes. 50.0 g (0.45 mol) of 4,6-dihydroxypyrimidine was slowly addedunder cooling with ice. After completion of the addition, when thetemperature-rising was terminated, the mixture was reacted at 90° C. for3 hours. Excess phosphorus oxychloride was distilled off under reducedpressure, and 300 ml of chloroform was added, and the mixture was slowlyadded into ice water. The organic layer was washed with an aqueoussodium hydrogencarbonate solution, water and an aqueous sodium chloridesolution in this order, dried and concentrated, and the obtained crudecrystals were washed with n-hexane to obtain 43.8 g (yield: 55%) of4,6-dichloropyrimidine-5-carboaldehyde as brown crystals (melting point:65-66° C.).

REFERENCE EXAMPLE 15 Preparation of4,6-dimethoxypyrimidine-5-carboaldehyde

43.6 g (246 mmol) of 4,6-dichloropyrimidine-5-carboaldehyde wasdissolved in 200 ml of methanol, and 120 g (622 mmol) of 28% sodiummethoxide was added under cooling with ice and then reacted for 2 hoursat room temperature. After completion of the reaction, the solvent wasdistilled off, and an aqueous citric acid solution was added, followedby extraction with ethyl acetate. The organic layer was washed with anaqueous sodium hydrogencarbonate solution, an aqueous citric acidsolution, water and an aqueous sodium chloride solution in this order,dried and concentrated, and the obtained crude crystals were washed withisopropyl ether to obtain 8.3 g (yield: 20%) of4,6-dimethoxypyrimidine-5-carboaldehyde.

REFERENCE EXAMPLE 16 Preparation of1-(4,6-dimethoxypyrimidin-5-yl)-3-methylbutan-2-ol

0.81 g (33 mmol) of magnesium was added to 30 ml of tetrahydrofuran, and4.1 g (33 mmol) of 2-bromopropane was added to prepare a tetrahydrofuransolution of isopropyl magnesium bromide. 2.8 g (17 mmol) of4,6-dimethoxypyrimidine-5-carboaldehyde was dissolved in 50 ml oftetrahydrofuran, and the solution was added to the above tetrahydrofuransolution at room temperature and reacted overnight. The reactionsolution was poured into an aqueous ammonium chloride solution andextracted with ethyl acetate. The organic layer was washed with anaqueous citric acid solution, water and an aqueous sodium chloridesolution in this order, dried and concentrated, and the obtained oilyproduct was purified by column chromatography (ethylacetate:n-hexane=1:4) to obtain 1.9 g (yield: 54%) of 1-(4,6-dimethoxypyrimidin-5-yl)-3-methylbutan-2-ol as slightly yellow crystals.

REFERENCE EXAMPLE 17 Preparation of5-(2-azide-3-methylbutyl)-4,6-dimethoxypyrimidine

1.05 g (5 mmol) of 1-(4,6-dimethoxypyrimidin-5-yl)-3-methylbutan-2-olwas dissolved in 10 ml of toluene, and under cooling with ice, 1.01 g(10 mmol) of trimethylsilylazide and 1.42 g (10 mmol) of borontrifluoride diethyl ether complex were added sequentially and thenreacted for 7 hours at room temperature. After completion of thereaction, the product was poured into water and extracted with toluene.The organic layer was washed with an aqueous sodium hydrogencarbonatesolution, water and an aqueous sodium chloride solution in this order,dried and concentrated, and the obtained oily product was purified bycolumn chromatography (ethyl actate:n-hexane=1:9) to obtain 1.22 g(yield: 100%) of 5-(2-azide-3-methylbutyl)-4,6-dimethoxypyrimidine ascolorless liquid.

[¹H-NMR (300 MHz CDCl₃, TMS δ (ppm)) 0.70 (3 H, d), 1.13 (3H, d), 2.44(1H, m), 4.00 (6H, s), 4.38 (1H, d), 8.39 (1H, s)].

REFERENCE EXAMPLE 18 Preparation of1-(4,6-dimethoxypyrimidin-5-yl)-2-methylpropylamine

1.2 g (5.1 mmol) of 5-(2-azide-3-methylbutyl)-4,6-dimethoxypyrimidinewas dissolved in 20 ml of methanol, and under cooling with ice, 1.5 g(0.062 mol) of magnesium was added and reacted overnight. Aftercompletion of the reaction, the solvent was distilled off, and ether wasadded. Insolubles were filtered off, followed by extraction with dilutedhydrochloric acid. An aqueous sodium hydroxide solution was added toalkaline, followed by extraction with toluene. The organic layer waswashed with water and an aqueous sodium chloride solution in this order,dried and concentrated, and the obtained oily product was purified bycolumn chromatography (ethyl acetate:n-hexane=1:1) to obtain 0.80 g(yield: 75%) of 1-(4,6-dimethoxypyrimidin-5-yl)-2-methylpropylamine ascolorless crystals.

[¹H-NMR (300 MHz, CDCl₃, TMS δ (ppm)) 0.70 (3 H, d), 1.07 (3H, d), 1.71(2H, s), 2.02 (1H, m), 3.78 (1H, d), 3.97 (6H, s), 8.33 (1H, s)].

Now, the physical properties (¹H-NMR values (CDCl₃/TMS δ (ppm)) of thecompounds of the present invention prepared in accordance with themethods disclosed in processes 1 to 12, will be shown in Tables 40 to43.

TABLE 40 Compound No. NMR (δ(ppm), 300MHz, TMS-CDCl₃) 1-016 0.81(3H, d),1.01(3H, d), 2.75-2.87(1 H, m), 2.90(1H, s), 3.60(2H, dd), 3.78(3 H, s),5.44(1H, d), 6.83(2H, d), 7.11(2 H, d), 9.23(1H, s), 9.25(1H, s) 1-0340.29-0.32(1H, m), 0.75-0.77(3H, m), 1.48-1.60(1H, m), 2.99(3H, s),3.70(2H, s), 4.84(1H, d), 7.17-7.33(5H, m), 9.25 (1H, s), 9.31(1H, s)1-195 0.76-0.81(3H, t, 3H, t), 0.91-0.98(3 H, t, 3H, t), 1.36-1.41(3H,d, 3H, d), 2.64-2.90(1H, m, 1H, m), 2.75(3H, s), 2.85 (3H, s),3.69-3.80(1H, q, 1H, q), 5.13(1 H, d), 5.51(1H, d), 7.17-7.31(5H, m, 5H,m), 9.22(1H, s), 9.23(1H, s), 9.27(1H, s), 9.30(1H, s), mixture ofdiastereoisomers 1-329 0.80(3H, d), 1.07(3H, d), 1.45(3H, s), 1.50(3H,s), 2.39(3H, s), 2.67-2.80(1 H, m), 5.58(1H, d), 7.08(2H, d), 7.25(2 H,d), 9.15(1H, s), 9.27(1H, s) 1-488 2.76(3H, s), 2.88(3H, s), 3.70(3H,s), 3.72(3H, s), 3.77(2H, s), 3.79(2H, s), 7.36-7.73(9H, m, 9H, m),8.57(1H, s), 8.61(1H, s), 9.25(1H, s), 9.27(1H, s), mixture ofdiastereoisomers 1-490 2.76(3H, s), 2.88(3H, s), 3.70(3H, s), 3.72(3H,s), 3.77(2H, s), 3.79(2H, s), 6.70-7.40(8H, m, 8H, m), 8.55(1H, s),8.60(1H, s), 9.25(1H, s), 9.27(1H, s), mixture of diastereoisomers 1-5260.89(3H, d), 0.98(3H, d), 2.48-2.60(1 H, m), 2.68(3H, s), 2.92(3H, s),3.63(2 H, s), 5.38(1H, d), 7.05-7.28(5H, m), 8.94(1H, s), 9.13(1H, s)

 

TABLE 41 Compound No. NMR (δ(ppm), 300MHz, TMS-CDCl₃) 1-562 0.79(3H, d),0.89(3H, d), 0.89(3H, d), 1.12(3H, t), 1.16(3H, d), 1.29(3H, t),1.25(3H, d), 1.52(3H, d), 1.88(1H, t), 2.27(1H, t), 2.04-2.94(3H, m, 3H,m), 3.44-3.56(1H, m, 1H, m), 3.69-3.81(2H, m), 3.90-4.00(2H, m),5.77(2H, d, 2H, d), 7.19-7.35(5H, m, 5H, m), 8.59(1H, s), 8.61(1H, s),9.00(1H, s), 9.08(1H, s), mixture of diastereoisomers 1-592 0.90(3H, d),1.01(3H, d), 1.36(3H, d), 2.53-2.65(1H, m), 2.73(3H, s), 3.78(1 H, q),4.01(3H, s), 5.70(1H, d), 6.99(2 H, d), 7.18(2H, d), 8.89(1H, s), 9.16(1H, s) 1-593 0.80(3H, d), 0.92(3H, d), 1.36(3H, d), 2.40-2.50(1H, m),2.62(3H, s), 3.68(1 H, q), 4.02(3H, s), 5.76(1H, d), 7.14(2 H, d),7.27(2H, d), 8.92(1H, s), 9.19(1 H, s) 1-595 0.80(3H, d), 0.91(3H, d),1.35(3H, d), 1.45(3H, t), 2.40-2.50(1H, m), 2.63(3 H, s), 3.67(1H, q),4.51(2H, q), 5.78(1 H, d), 7.14(2H, d), 7.27(2H, d), 8.92(1 H, s),9.19(1H, s) 1-651 0.94(3H, t, 3H, t), 1.47(3H, d), 1.66(3 H, d),1.88-1.98(2H, m, 2, m), 2.08(3H, s), 2.09(3H, s), 2.61(3H, s), 2.68(3H,s), 3.74(2H, dd, 2H, dd), 4.29(1H, q, 1H, q), 6.03(1H, t), 6.12(1H, t),7.23-7.37 (5H, m, 5H, m), 8.61(1H, s), 8.63(1H, s), 9.09(1H, s),9.11(1H, s), mixture of diastereoisomers 1-652 0.94(3H, t, 3H, t),1.49(3H, d), 1.65(3 H, d), 1.91-1.99(2H, m, 2H, m), 2.07(3H, s),2.63(3H, s), 2.70(3H, s), 3.70(2H, s, 2H, s), 4.25-4.32(1H, m, 1H, m),6.01 (1H, t), 6.11(1H, t), 6.99-7.28(4H, m, 4 H, m), 8.62(1H, s),8.64(1H, s), 9.10(1 H, s), 9.11(1H, s), mixture of diastereoisomers

 

TABLE 42 Compound No. NMR (δ(ppm), 300MHz, TMS-CDCl₃) 1-872 0.77(3H, d),0.97(3H, d), 1.37(3H, d), 2.85(3H, s), 2.81-2.91(1H, m), 3.77(1 H,q)5.14(1H, d), 7.16-7.29(5H, m)9.22 (1H, s), 9.29(1H, s) 1-873 0.80(3H,d), 1.15(3H, d), 2.43(3H, s), 2.76-2.84(1H, m), 3.18(3H, s), 5.23(1 H,d), 6.77(2H, d), 7.02(1H, t), 7.15(2 H, d), 9.16(1H, s), 9.26(1H, s)1-877 0.82(3H, t), 0.93(3H, t), 1.72(3H, s), 1.78(3H, s), 1.86-1.92(2H,m), 2.77(3 H, s), 3.01(3H, s), 3.70(2H, s), 4.06(2 H, s), 3.70-4.20(4H,m), 5.86(1H, t), 6.09(1H, t), 7.14-7.30(4H, m), 8.70(1H, s), 8.80(1H,s), 9.13(1H, s), 9.22(1H, s) 1-878 0.89(3H, t), 0.97(3H, t), 1.70-1.90(2H, m), 1.90-2.10(2H, m), 2.66(3H, s), 2.70(3H, s), 2.94(3H, s), 3.00(3H,s), 3.62 (2H, s), 3.73(2H, dd), 5.62(1H, t), 5.70-5.79(1H, m),7.05-7.27(4H, m, 4H, m), 8.68(1H, s), 8.83(1H, s), 9.15(1H, s), 9.20(1H,s) 2-58 0.44-0.53(2H, m), 0.55-0.65(H, m), 1.16(3H, s), 3.13(3H, s),3.80(2H, s), 5.64 (1H, s), 6.63(1H, d), 6.75(1H, d), 9.12 (1H, s),9.26(1H, s) 2-75 0.89(3H, d), 0.99(3H, d), 1.23(3H, t), 2.43-2.51(1H,m), 2.71-3.05(2H, m), 2.77(3H, s), 3.80(2H, dd), 5.72(1H, d), 6.65 (1H,d), 6.74(1H, d), 8.61(1H, s), 9.06 (1H, s)

 

TABLE 43 Compound No. NMR (δ(ppm), 300MHz, TMS-CDCl₃) 4-26 0.78(3H, t),1.11-1.21(3H, m), 1.31(3 H, t), 2.36(3H, s), 2.58(3H, s), 2.44-2.67 (1H,m), 2.77(3H, s), 2.86(3H, s), 2.88-3.16 (2H, m), 5.02(1H, dd), 7.04-7.45(4H, m), 8.52(1H, s), 8.69(1H, s), 9.01 (1H, s), 9.10(1H, s) 4-280.77(3H, d), 1.15(3H, d), 1.31(3H, t), 2.31(3H, s), 2.33-2.43(1H,m)2.80(3H, s), 2.89-3.17(2H, m), 5.02(1H, d), 7.22-7.35 (4H, m),8.52(1H, s), 9.01(1H, s) 4-36 0.77(3H, d), 1.12(3H, d), 2.48-2.58(1 H,m), 3.04(3H, s), 5.09(1H, d), 7.35-7.39 (2H, m), 7.46-7.54(3.H,m)9.05(1H, s), 9.21(1H, s) 4-37 0.77(3H, d), 1.13(3H, d), 2.53-2.59(1H,), 3.02(3H, s), 5.1(1H, d), 7.04-7.08 (2H, m), 7.54-7.58(2H,m)9.06(1H, s), 9.24(1H, s) 4-54 0.86(3H, t), 1.34(3H, t), 1.63-2.09(2 H,m), 2.76(3H, s), 2.91-3.09(2H, m), 5.27 (1H, dd)7.17-7.21(2H,m)7.72-7.79 (2H, m), 8.47(1H, s), 9.06(1H, s) 5-13 0.79(3H, d), 1.16(3H,d), 1.83-1.90(2H, m), 2.91-2.99(1H, m), 3.07-3.14(3H, m), 3.32-3.40(1H,m), 4.40(1H, d), 4.68(1H, d), 5.02(1H, d)7.20-7.33(5H, m), 9.25 (1H, s),9.46(1H, s)

 

The herbicide of the present invention comprises the pyrimidinederivative represented by the formula [I] as an active ingredient.

In order to use the compound of the present invention as a herbicide,the compound of the present invention may be used by itself, but it maybe used as formulated in e.g. a dust, a wettable powder, an emulsifiableconcentrate, a microgranule or a granule by incorporating a carrier, asurfactant, a dispersant or an adjuvant which are commonly used forformulations. The carrier to be used for formulation may, for example,be a solid carrier such as talc, bentonite, clay, kaolin, diatomaceousearth, white carbon, vermiculite, calcium carbonate, slaked lime, silicasand, ammonium sulfate or urea, or a liquid carrier such as isopropylalcohol, xylene, cyclohexane or methylnaphthalene.

The surfactant and the dispersant may, for example, be a metal salt ofan alkylbenzene sulfonic acid, a metal salt ofdinaphthylmethanedisulfonic acid, an alcohol/sulfuric acid ester, analkylaryl sulfonate, lignin sulfonate, polyoxyethylene glycol ether,polyoxyethylene alkylaryl ether, and polyoxyethylene sorbitanmonoalkylate. The adjuvant may, for example, be carboxymethylcellulose,polyethylene glycol or gum Arabic. In the actual use, it may be appliedas diluted to a proper concentration or may be directly applied.

The herbicide of the present invention can be used by application tofoliage, application to soil or application to water surface. The blendproportion of the active ingredient may suitably be selected, as thecase requires. However, in the case of a dust or a granule, it ispreferably selected within a range of from 0.01 to 10% (weight),preferably from 0.05 to 5% (weight). Further, in the case of anemulsifiable concentrate and a wettable powder, it is preferablyselected within a range of from 1 to 50% (weight), preferably from 5 to30% (weight).

The dose of the herbicide of the present invention varies depending uponthe type of the compound to be used, the objective weeds, thegermination tendency, the environmental conditions as well as theformulation to be used. However, when it is used as it is, in the caseof a dust or a granule, the dose is preferably selected within a rangeof from 0.1 g to 5 kg, preferably from 1 g to 1 kg, per 10 ares as anactive ingredient. Further, in a case where it is used in a liquid stateas in the case of an emulsifiable concentrate or wettable powder, thedose is preferably selected within a range of from 0.1 to 50,000 ppm,preferably from 10 to 10,000 ppm.

Further, the compound of the present invention may be used incombination with an insecticide, a fungicide, another herbicide, a plantgrowth regulator, a fertilizer, etc., as the case requires.

Now, the formulation method will be described in detail with referenceto typical Formulation Examples. However, the compounds, the types ofthe additives and the blend ratios are not limited thereto and may bevaried within wide ranges. In the following description, “parts” means“parts by weight”.

FORMULATION EXAMPLE 1: WETTABLE POWDER

To 10 parts of compound (1-8), 0.5 part of polyoxyethyleneoctylphenylether, 0.5 part of a sodium salt of β-naphthalene sulfonic acid formalincondensate, 20 parts of diatomaceous earth and 69 parts of clay weremixed and pulverized to obtain a wettable powder.

FORMULATION EXAMPLE 2: WETTABLE POWDER

To 10 parts of compound (1-8), 0.5 part of polyoxyethyleneoctylphenylether, 0.5 part of a sodium salt of β-naphthalene sulfonic acid formalincondensate, 20 parts of diatomaceous earth, 5 parts of white carbon and64 parts of clay were mixed and pulverized to obtain a wettable powder.

FORMULATION EXAMPLE 3: WETTABLE POWDER

To 10 parts of compound (1-8), 0.5 part of polyoxyethyleneoctylphenylether, 0.5 part of a sodium salt of β-naphthalene sulfonic acid formalincondensate, 20 parts of diatomaceous earth, 5 parts of white carbon and64 parts of calcium carbonate, were mixed and pulverized to obtain awettable powder.

FORMULATION EXAMPLE 4: EMULSIFIABLE CONCENTRATE

To 30 parts of compound (1-8), 60 parts of a mixture of equal amounts ofxylene and isophorone, and 10 parts of a mixture comprising a surfactantpolyoxyethylenesorbitan alkylate, a polyoxyethylene alkylaryl polymerand an alkylaryl sulfonate, were added, followed by thorough stirring toobtain an emulsifiable concentrate.

FORMULATION EXAMPLE 5: GRANULE

10 parts of compound (1-8), 80 parts of an extender having talc andbentonite mixed in a ratio of 1:3, 5 parts of white carbon, 5 parts of amixture comprising a surfactant polyoxyethylenesorbitan alkylate, apolyoxyethylene alkylaryl polymer and an alkylaryl sulfonate, and 10parts of water were mixed and thoroughly kneaded to obtain a paste,which was extruded through a screen having openings having a diameter of0.7 mm, then dried and cut into a length of from 0.5 to 1 mm to obtain agranule.

Now, the effects of the compound of the present invention will bedescribed with reference to Test Examples.

TEST EXAMPLE 1: TESTS OF HERBICIDAL EFFECTS BY FLOODED PADDY FIELDTREATMENT

In a 100 cm² plastic pot, paddy field soil was filled and paddled. Then,seeds of barnyard grass (Eo) and monochoria (Mo) were sown, and waterwas introduced to a depth of 3 cm. Next day, a wettable powder preparedin accordance with Formulation Example 1 was diluted with water anddropwise applied to the water surface. The dose was 100 g of the activeingredient per 10 ares. Thereafter, cultivation was carried out in agreen house, and on the 21st day after the treatment, the herbicidaleffects were examined in accordance with the standards as identified inTable 44. The results are shown in Tables 45 to 52.

TABLE 44 Herbicidal effects (growth- inhibition degree) and Index numberphytotoxity 5 Herbicidal effect or phytotoxity for controlling more than90% 4 Herbicidal effect or phytotoxity of at least 70% and less than 90%3 Herbicidal effect or phytotoxity of at least 50% and less than 70% 2Herbicidal effect or phytotoxity of at least 30% and less than 50% 1Herbicidal effect or phytotoxity of at least 10% and less than 30% 0Herbicidal effect or phytotoxity of at least 0% and less than 10%

 

TABLE 45 Compound No. Dose (gai/10a) Eo Mo 1-4 100 5 5 1-8 100 5 5 1-9100 5 5 1-10 100 5 5 1-12 100 5 5 1-13 100 5 5 1-15 100 5 5 1-16 100 5 51-17 100 5 5 1-18 100 5 5 1-19 100 5 5 1-20 100 5 5 1-21 100 5 5 1-22100 5 5 1-23 100 5 5 1-24 100 5 5 1-25 100 5 5 1-26 100 5 5 1-27 100 5 51-32 100 5 5 1-33 100 5 5 1-34 100 5 5 1-35 100 5 5 1-36 100 5 5 1-37100 5 5 1-38 100 5 5 1-39 100 5 5 1-40 100 5 5 1-41 100 5 5 1-42 100 5 51-43 100 5 5 1-44 100 5 5 1-45 100 5 5 1-46 100 5 5 1-47 100 5 5 1-48100 5 5 1-49 100 5 5 1-50 100 5 5 1-51 100 5 5 1-52 100 5 5 1-53 100 5 51-54 100 5 5 1-55 100 5 5 1-56 100 5 5 1-57 100 5 5 1-58 100 5 5 1-59100 5 5 1-60 100 5 5 1-61 100 5 5 1-62 100 5 5 1-63 100 5 5 1-64 100 5 51-65 100 5 5

 

TABLE 46 Compound No. Dose (gai/10a) Eo Mo 1-66 100 5 5 1-67 100 5 51-68 100 5 5 1-70 100 5 5 1-71 100 5 5 1-72 100 5 5 1-74 100 5 5 1-75100 5 5 1-76 100 5 5 1-78 100 5 5 1-80 100 5 5 1-81 100 5 5 1-82 100 5 51-83 100 5 5 1-84 100 5 5 1-85 100 5 5 1-86 100 5 5 1-87 100 5 5 1-88100 5 5 1-89 100 5 5 1-90 100 5 5 1-91 100 5 5 1-93 100 5 5 1-94 100 5 51-95 100 5 5 1-96 100 5 5 1-97 100 5 5 1-98 100 5 5 1-99 100 5 5 1-100100 5 5 1-101 100 5 5 1-102 100 5 5 1-103 100 5 5 1-104 100 5 5 1-105100 5 5 1-106 100 5 5 1-107 100 5 5 1-111 100 5 4 1-112 100 5 5 1-113100 5 5 1-114 100 5 5 1-115 100 5 5 1-116 100 5 5 1-118 100 5 5 1-119100 5 5 1-120 100 5 5 1-121 100 5 5 1-122 100 5 5 1-123 100 5 5 1-124100 5 5 1-125 100 5 5 1-126 100 5 5 1-127 100 5 5

 

TABLE 47 Compound No. Dose (gai/10a) Eo Mo 1-128 100 5 4 1-129 100 5 51-130 100 5 5 1-131 100 5 5 1-132 100 5 5 1-133 100 5 5 1-134 100 5 51-135 100 5 5 1-136 100 5 5 1-137 100 5 5 1-138 100 5 5 1-139 100 5 51-140 100 5 5 1-141 100 5 5 1-142 100 5 5 1-143 100 5 5 1-144 100 5 51-145 100 5 5 1-146 100 5 5 1-147 100 5 5 1-148 100 5 5 1-150 100 5 51-151 100 5 5 1-152 100 5 5 1-153 100 5 5 1-154 100 5 5 1-155 100 5 51-156 100 5 5 1-159 100 5 5 1-160 100 5 5 1-161 100 5 5 1-162 100 5 51-163 100 5 5 1-164 100 5 5 1-165 100 5 5 1-166 100 5 5 1-167 100 5 51-168 100 5 5 1-169 100 5 5 1-170 100 5 5 1-171 100 5 5 1-172 100 5 51-173 100 5 5 1-174 100 5 5 1-175 100 5 5 1-177 100 5 5 1-178 100 5 41-180 100 5 5 1-181 100 5 5 1-182 100 5 5 1-183 100 5 5 1-184 100 5 51-185 100 5 5

 

TABLE 48 Compound No. Dose (gai/10a) Eo Mo 1-186 100 5 5 1-187 100 5 51-188 100 5 5 1-189 100 5 5 1-190 100 5 5 1-191 100 5 5 1-192 100 5 51-193 100 5 5 1-194 100 5 5 1-195 100 5 5 1-196 100 5 5 1-197 100 5 51-198 100 5 5 1-200 100 5 5 1-214 100 5 5 1-217 100 5 5 1-218 100 5 51-219 100 5 5 1-220 100 5 5 1-221 100 5 5 1-222 100 5 5 1-225 100 5 51-226 100 5 5 1-228 100 5 5 1-234 100 5 5 1-249 100 5 5 1-250 100 5 51-251 100 5 5 1-254 100 5 5 1-265 100 5 5 1-266 100 5 5 1-267 100 5 51-270 100 5 5 1-273 100 5 5 1-274 100 5 5 1-305 100 5 5 1-306 100 5 51-307 100 5 5 1-310 100 5 5 1-321 100 5 5 1-322 100 5 5 1-323 100 5 51-324 100 5 5 1-325 100 5 5 1-327 100 5 5 1-328 100 5 5 1-329 100 5 51-330 100 5 5 1-331 100 5 5 1-333 100 5 5 1-334 100 5 5 1-335 100 5 51-401 100 5 5

 

TABLE 49 Compound No. Dose (gai/10a) Eo Mo 1-402 100 5 5 1-403 100 5 51-404 100 5 5 1-407 100 5 5 1-409 100 5 5 1-410 100 5 5 1-411 100 5 51-412 100 5 5 1-413 100 5 5 1-414 100 5 5 1-415 100 5 5 1-416 100 5 51-417 100 5 5 1-418 100 5 5 1-419 100 5 5 1-420 100 5 5 1-421 100 5 51-422 100 5 5 1-424 100 5 5 1-425 100 5 5 1-426 100 5 5 1-427 100 5 51-428 100 5 5 1-429 100 5 5 1-430 100 5 5 1-431 100 5 5 1-432 100 5 51-433 100 5 5 1-434 100 5 5 1-435 100 5 5 1-436 100 5 5 1-437 100 5 51-438 100 5 5 1-439 100 5 5 1-441 100 5 5 1-442 100 5 5 1-443 100 5 51-444 100 5 5 1-445 100 5 5 1-446 100 5 5 1-447 100 5 5 1-448 100 5 51-449 100 5 5 1-450 100 5 5 1-451 100 5 5 1-452 100 5 5 1-454 100 5 51-455 100 5 5 1-458 100 5 5 1-459 100 5 5 1-460 100 5 5 1-461 100 5 51-463 100 5 5

 

TABLE 50 Compound No. Dose (gai/10a) Eo Mo 1-464 100 5 5 1-465 100 5 51-469 100 5 5 1-473 100 5 5 1-476 100 5 5 1-482 100 5 5 1-483 100 5 51-484 100 5 5 1-485 100 5 5 1-486 100 5 5 1-487 100 5 5 1-488 100 5 51-489 100 5 5 1-490 100 5 5 1-491 100 5 5 1-492 100 5 5 1-493 100 5 51-494 100 5 5 1-495 100 5 5 1-496 100 5 5 1-497 100 5 5 1-498 100 5 51-499 100 5 5 1-500 100 5 5 1-501 100 5 5 1-502 100 5 5 1-504 100 5 51-505 100 5 5 1-506 100 5 5 1-507 100 5 5 1-510 100 5 5 1-511 100 5 51-517 100 5 5 1-518 100 5 5 1-519 100 5 5 1-520 100 5 5 1-521 100 5 51-524 100 5 5 1-526 100 5 5 1-527 100 5 5 1-528 100 5 5 1-529 100 5 51-530 100 5 5 1-532 100 5 5 1-533 100 5 5 1-535 100 5 5 1-536 100 5 51-537 100 5 5 1-538 100 5 5 1-539 100 5 5 1-540 100 5 5 1-541 100 5 51-546 100 5 5

 

TABLE 51 Compound No. Dose (gai/10a) Eo Mo 1-547 100 5 5 1-548 100 5 51-549 100 5 5 1-550 100 5 5 1-551 100 5 5 1-553 100 5 5 1-555 100 5 51-558 100 5 5 1-559 100 5 5 1-560 100 5 5 1-561 100 5 5 1-562 100 5 51-563 100 5 5 1-565 100 5 5 1-566 100 5 5 1-567 100 5 5 1-569 100 5 51-571 100 5 4 1-572 100 5 5 1-573 100 5 5 1-579 100 5 5 1-584 100 5 51-586 100 5 5 1-589 100 5 5 1-591 100 5 5 1-592 100 5 5 1-593 100 5 51-594 100 5 5 1-595 100 5 5 1-597 100 5 5 1-598 100 5 5 1-599 100 5 51-600 100 5 5 1-602 100 5 5 1-603 100 5 5 1-604 100 5 5 1-606 100 5 51-607 100 5 5 1-608 100 5 5 1-609 100 5 5 1-611 100 5 5 1-614 100 5 51-615 100 5 5 1-624 100 5 5 1-626 100 5 5 1-627 100 5 5 1-637 100 5 51-639 100 5 5 1-640 100 5 5 1-641 100 5 5 2-1 100 5 5 2-2 100 5 5 2-3100 5 5

 

TABLE 52 Compound No. Dose (gai/10a) Eo Mo 2-5 100 5 5 2-6 100 5 5 2-7100 5 5 2-8 100 5 5 2-9 100 5 5 2-10 100 5 5 2-11 100 5 5 2-12 100 5 52-13 100 5 5 2-14 100 5 5 2-19 100 5 5 2-20 100 5 5 2-23 100 5 5 2-24100 5 5 2-25 100 5 5 2-31 100 5 5 2-32 100 5 5 2-41 100 5 5 2-42 100 5 52-44 100 5 5 2-46 100 5 5 2-48 100 5 5 2-50 100 5 5 2-51 100 5 5 2-52100 5 5 2-53 100 5 5 2-54 100 5 5 2-55 100 5 5 2-56 100 5 5 2-57 100 5 52-58 100 5 5 2-59 100 5 5 2-60 100 5 5 2-61 100 5 5 2-62 100 5 5 2-63100 5 5 2-71 100 5 5 2-72 100 5 5 2-73 100 5 5 2-74 100 5 5 2-75 100 5 52-77 100 5 5 2-78 100 5 5 2-80 100 5 4 4-1 100 5 5 4-2 100 5 5

 

TEST EXAMPLE 2: TEST OF HERBICIDAL EFFECTS BY UPLAND SOIL TREATMENT

In a 80 cm² plastic pot, upland soil was filled, and seeds of barnyardgrass (Ec) and green foxtail (Se) were sown and covered with soil. Awettable powder prepared in accordance with Formulation Example 1 wasdiluted with water and uniformly applied to the soil surface by means ofa small size spray at a rate of 100 l per 10 ares, so that the dose ofthe active ingredient would be 100 g per 10 ares. Thereafter,cultivation was carried out in a green house, and on the 21st day afterthe treatment, the herbicidal effects were examined in accordance withthe standards as identified in Table 44. The results are shown in Tables53 to 60.

TABLE 53 Compound No. Dose (gai/10a) Ec Se 1-8 100 5 5 1-9 100 5 5 1-10100 4 4 1-12 100 5 5 1-13 100 5 5 1-15 100 5 5 1-16 100 4 5 1-17 100 4 41-20 100 5 5 1-21 100 5 5 1-22 100 5 5 1-23 100 5 5 1-24 100 5 5 1-25100 5 5 1-26 100 5 5 1-27 100 5 5 1-32 100 5 5 1-33 100 5 5 1-34 100 5 51-35 100 5 5 1-36 100 5 5 1-37 100 5 5 1-38 100 5 4 1-40 100 5 4 1-41100 5 5 1-42 100 5 5 1-45 100 5 5 1-46 100 5 5 1-47 100 5 5 1-48 100 5 51-49 100 5 4 1-50 100 5 5 1-51 100 5 5 1-52 100 5 5 1-53 100 5 5 1-54100 5 5 1-55 100 5 5 1-56 100 5 5 1-57 100 5 5 1-58 100 5 5 1-59 100 5 51-60 100 5 5 1-61 100 5 5 1-62 100 4 4 1-63 100 5 5 1-64 100 5 5 1-65100 5 5 1-66 100 5 5 1-67 100 5 5 1-68 100 5 5 1-70 100 5 5 1-71 100 5 51-72 100 5 4

 

TABLE 54 Compound No. Dose (gai/10a) Ec Se 1-74 100 5 5 1-75 100 5 51-76 100 5 5 1-77 100 5 5 1-78 100 5 5 1-80 100 5 5 1-81 100 5 5 1-83100 5 5 1-85 100 5 5 1-87 100 5 5 1-88 100 5 5 1-89 100 5 5 1-90 100 5 51-91 100 4 5 1-92 100 5 5 1-95 100 5 5 1-96 100 5 5 1-97 100 5 5 1-98100 5 5 1-99 100 5 5 1-100 100 5 5 1-101 100 5 5 1-102 100 5 5 1-103 1005 5 1-105 100 5 5 1-106 100 5 4 1-11 100 5 5 1-112 100 5 5 1-113 100 5 41-114 100 5 5 1-115 100 5 5 1-116 100 5 4 1-118 100 5 5 1-119 100 5 41-120 100 5 4 1-121 100 5 4 1-122 100 5 5 1-123 100 5 5 1-124 100 5 51-125 100 5 5 1-126 100 5 5 1-127 100 5 5 1-128 100 5 5 1-130 100 5 51-131 100 5 5 1-133 100 5 5 1-134 100 5 5 1-135 100 5 5 1-136 100 5 51-137 100 5 5 1-138 100 5 5 1-139 100 5 5 1-140 100 5 5

 

TABLE 55 Compound No. Dose (gai/10a) Ec Se 1-141 100 5 5 1-142 100 5 51-143 100 5 5 1-144 100 5 5 1-145 100 5 5 1-146 100 4 4 1-147 100 5 51-148 100 5 5 1-150 100 5 5 1-151 100 5 5 1-152 100 5 5 1-153 100 5 51-155 100 4 4 1-159 100 5 5 1-160 100 5 5 1-161 100 5 5 1-162 100 5 41-163 100 5 5 1-164 100 5 5 1-165 100 5 5 1-166 100 5 5 1-167 100 5 51-168 100 5 5 1-169 100 5 5 1-170 100 5 5 1-171 100 5 4 1-172 100 5 51-173 100 5 5 1-174 100 5 5 1-177 100 4 4 1-180 100 5 5 1-181 100 5 51-182 100 5 5 1-186 100 5 5 1-187 100 5 5 1-190 100 4 4 1-192 100 5 51-193 100 5 5 1-194 100 5 5 1-195 100 5 5 1-196 100 5 5 1-197 100 5 51-198 100 5 5 1-200 100 5 5 1-214 100 5 5 1-217 100 5 5 1-218 100 5 51-219 100 5 5 1-220 100 5 5 1-222 100 5 5 1-225 100 5 5 1-226 100 5 41-228 100 5 5

 

TABLE 56 Compound No. Dose (gai/10a) Ec Se 1-234 100 5 5 1-249 100 5 51-250 100 4 5 1-251 100 5 5 1-254 100 5 5 1-265 100 5 5 1-266 100 5 51-267 100 5 5 1-270 100 5 5 1-273 100 5 5 1-274 100 5 5 1-305 100 5 51-306 100 5 5 1-307 100 5 5 1-310 100 5 5 1-321 100 5 5 1-323 100 4 41-326 100 4 4 1-327 100 5 5 1-328 100 5 5 1-329 100 5 5 1-330 100 5 51-331 100 5 5 1-332 100 5 5 1-333 100 5 5 1-334 100 5 5 1-335 100 5 51-401 100 5 5 1-402 100 5 5 1-403 100 5 5 1-404 100 5 5 1-407 100 5 51-409 100 5 5 1-410 100 5 5 1-411 100 5 5 1-412 100 5 5 1-414 100 4 51-416 100 5 5 1-417 100 5 5 1-418 100 5 5 1-419 100 5 5 1-424 100 5 51-425 100 5 5 1-426 100 5 5 1-427 100 5 5 1-428 100 5 5 1-429 100 5 51-430 100 5 5 1-431 100 5 5 1-432 100 5 5 1-433 100 5 5 1-434 100 5 51-435 100 5 5

 

TABLE 57 Compound No. Dose (gai/10a) Ec Se 1-436 100 5 5 1-437 100 5 51-438 100 5 5 1-439 100 5 4 1-441 100 5 5 1-442 100 5 5 1-443 100 5 51-444 100 5 5 1-445 100 5 5 1-446 100 5 5 1-447 100 5 5 1-448 100 5 41-449 100 5 5 1-450 100 5 5 1-451 100 5 5 1-452 100 5 5 1-454 100 4 51-455 100 5 5 1-458 100 5 4 1-459 100 5 5 1-460 100 5 5 1-461 100 5 51-463 100 4 5 1-464 100 5 5 1-465 100 5 5 1-466 100 4 4 1-471 100 5 41-473 100 5 4 1-476 100 5 5 1-482 100 5 5 1-483 100 5 4 1-484 100 5 51-485 100 5 5 1-488 100 5 5 1-489 100 5 5 1-490 100 5 5 1-492 100 5 51-493 100 5 5 1-494 100 5 5 1-495 100 5 5 1-496 100 5 4 1-497 100 5 51-498 100 5 5 1-499 100 5 4 1-502 100 4 4 1-504 100 5 5 1-505 100 5 51-506 100 5 5 1-507 100 5 5 1-508 100 5 5 1-511 100 4 4 1-517 100 5 51-518 100 5 5

 

TABLE 58 Compound No. Dose (gai/10a) Ec Se 1-519 100 5 5 1-520 100 5 51-521 100 5 5 1-523 100 4 5 1-524 100 5 5 1-526 100 5 5 1-527 100 5 51-528 100 5 5 1-529 100 5 5 1-530 100 5 5 1-531 100 4 4 1-532 100 5 51-533 100 5 5 1-535 100 5 5 1-536 100 5 5 1-537 100 5 5 1-538 100 5 51-539 100 5 5 1-540 100 5 5 1-541 100 5 4 1-546 100 5 5 1-547 100 5 51-548 100 5 5 1-549 100 5 5 1-550 100 5 5 1-551 100 5 5 1-553 100 5 51-555 100 5 5 1-558 100 5 5 1-559 100 5 5 1-560 100 5 5 1-561 100 5 41-562 100 5 5 1-563 100 5 5 1-565 100 5 5 1-566 100 5 5 1-567 100 5 51-569 100 5 5 1-571 100 5 5 1-572 100 5 5 1-573 100 5 4 1-579 100 5 51-584 100 5 5 1-586 100 5 5 1-589 100 5 5 1-591 100 5 5 1-592 100 5 51-594 100 5 5 1-597 100 4 4 1-598 100 5 4 1-600 100 4 5 1-602 100 5 51-603 100 4 4

 

TABLE 59 Compound No. Dose (gai/10a) Ec Se 1-604 100 5 4 1-606 100 5 51-607 100 4 4 1-608 100 5 5 1-609 100 5 4 1-611 100 5 5 1-614 100 5 51-616 100 5 5 1-617 100 5 5 1-618 100 5 5 1-619 100 5 5 1-620 100 5 51-621 100 5 5 1-622 100 4 5 1-623 100 5 4 1-624 100 5 5 1-625 100 4 51-626 100 5 4 1-627 100 5 5 1-636 100 4 4 1-639 100 5 5 1-640 100 4 41-641 100 5 4 1-642 100 4 4 1-646 100 4 4 2-1 100 5 4 2-2 100 5 4 2-6100 5 4 2-7 100 5 5 2-8 100 5 5 2-9 100 5 5 2-10 100 5 5 2-11 100 5 52-12 100 5 5 2-13 100 5 5 2-14 100 5 5 2-19 100 5 5 2-20 100 5 5 2-23100 5 5 2-24 100 5 5 2-25 100 5 5 2-31 100 5 5 2-32 100 5 5 2-44 100 5 52-46 100 5 5 2-47 100 4 5 2-50 100 5 5 2-51 100 5 5 2-52 100 5 5 2-53100 5 5 2-54 100 5 5 2-55 100 5 5 2-56 100 5 5

 

TABLE 60 Compound No. Dose (gai/10a) Ec Se 2-57 100 5 5 2-58 100 5 52-59 100 5 4 2-60 100 5 5 2-61 100 5 5 2-62 100 5 5 2-63 100 5 4 2-71100 5 5 2-72 100 5 5 2-73 100 5 5 2-74 100 5 5 2-75 100 5 5 2-77 100 5 52-78 100 5 5 2-79 100 5 5 4-1 100 5 5 4-2 100 5 4

 

TEST EXAMPLE 3: TEST OF HERBICIDAL EFFECTS BY FOLIAGE TREATMENT INUPLAND FIELD

In a 80 cm² plastic pot, upland soil was filled, and seeds of barnyardgrass (Ec) and green foxtail (Se) were sown and cultured in a greenhouse for 2 weeks. Then, a wettable powder prepared in accordance withFormulation Example 1 was diluted with water and applied to the entirefoliage from above the plants by means of a small size spray at a rateof 100 l per 10 ares so that the dose of the active ingredient would be100 g per 10 ares. Thereafter, cultivation was carried out in a greenhouse, and on the 14th day after the treatment, the herbicidal effectswere examined in accordance with the standards of Table 44. The resultsare shown in Tables 61 to 64.

TABLE 61 Compound No. Dose (gai/10A) Ec Se 1-1 100 4 4 1-8 100 5 4 1-9100 5 4 1-10 100 4 4 1-12 100 5 4 1-13 100 5 4 1-21 100 4 4 1-22 100 4 41-24 100 4 4 1-26 100 4 4 1-27 100 4 4 1-41 100 5 4 1-42 100 4 4 1-46100 4 4 1-47 100 4 4 1-48 100 5 4 1-50 100 4 4 1-53 100 4 4 1-54 100 5 41-55 100 4 4 1-56 100 4 4 1-57 100 5 4 1-58 100 4 4 1-59 100 4 4 1-60100 4 4 1-61 100 4 4 1-66 100 5 4 1-78 100 5 4 1-81 100 4 4 1-83 100 5 41-87 100 4 4 1-88 100 4 4 1-89 100 5 4 1-92 100 5 4 1-95 100 5 5 1-96100 5 5 1-98 100 4 4 1-100 100 5 5 1-107 100 4 4 1-111 100 4 4 1-112 1004 5 1-113 100 4 4 1-122 100 4 4 1-127 100 4 4 1-129 100 5 5 1-133 100 54 1-137 100 5 4 1-142 100 4 4 1-143 100 4 4 1-144 100 4 4 1-152 100 4 41-153 100 4 4 1-164 100 4 4

 

TABLE 62 Compound No. Dose (gai/10d) Ec Se 1-172 100 5 5 1-186 100 5 41-192 100 4 4 1-193 100 5 4 1-194 100 5 4 1-195 100 5 4 1-196 100 5 41-198 100 4 4 1-214 100 4 4 1-218 100 4 4 1-220 100 5 5 1-221 100 4 41-251 100 4 4 1-267 100 4 4 1-270 100 4 4 1-330 100 4 4 1-331 100 4 41-333 100 4 4 1-334 100 4 4 1-401 100 5 5 1-402 100 5 4 1-403 100 4 41-404 100 5 4 1-407 100 4 4 1-409 100 4 4 1-410 100 4 4 1-411 100 4 41-412 100 4 4 1-416 100 5 4 1-417 100 4 5 1-419 100 4 5 1-424 100 4 41-426 100 4 4 1-427 100 4 4 1-428 100 4 4 1-430 100 4 4 1-431 100 4 41-432 100 5 4 1-434 100 4 4 1-435 100 4 4 1-436 100 4 4 1-437 100 4 41-441 100 4 4 1-442 100 4 4 1-445 100 5 5 1-446 100 5 4 1-447 100 5 41-449 100 4 4 1-450 100 4 4 1-451 100 4 4 1-452 100 4 4 1-454 100 4 41-455 100 4 4

 

TABLE 63 Compound No. Dose (gai/10a) Ec Se 1-459 100 4 4 1-461 100 4 41-463 100 4 4 1-464 100 4 4 1-473 100 5 4 1-482 100 5 4 1-484 100 5 51-486 100 4 4 1-488 100 5 4 1-489 100 4 4 1-490 100 4 4 1-492 100 5 41-493 100 4 4 1-494 100 5 4 1-496 100 4 4 1-497 100 4 4 1-504 100 5 41-505 100 5 5 1-506 100 4 4 1-507 100 4 4 1-508 100 4 4 1-517 100 4 41-519 100 4 4 1-526 100 5 4 1-527 100 4 4 1-528 100 4 4 1-529 100 5 41-530 100 4 4 1-532 100 5 4 1-536 100 4 4 1-537 100 4 4 1-538 100 4 41-539 100 4 4 1-540 100 4 4 1-541 100 4 4 1-546 100 4 4 1-547 100 4 41-558 100 4 4 1-559 100 4 4 1-560 100 4 4 1-661 100 5 4 1-563 100 5 41-565 100 5 4 1-566 100 4 4 1-569 100 5 4 1-571 100 4 4 1-572 100 4 41-579 100 4 4 1-584 100 4 4 1-586 100 5 4 1-589 100 4 4 1-591 100 4 41-592 100 5 4

 

TABLE 64 Compound No. Dose (gai/10a) Ec Se 1-594 100 5 5 1-598 100 4 41-600 100 5 4 1-602 100 4 4 1-606 100 4 4 1-607 100 4 4 1-609 100 4 41-611 100 4 4 1-617 100 4 4 1-619 100 4 4 1-622 100 4 4 1-642 100 4 42-11 100 5 4 2-12 100 5 4 2-23 100 4 4 2-25 100 5 4 2-46 100 4 4 2-50100 4 4 2-51 100 4 4 2-53 100 4 4 2-57 100 5 5 2-60 100 4 4 2-61 100 4 42-62 100 4 4 2-71 100 5 4 2-74 100 4 4 2-75 100 5 4 2-79 100 4 4 4-2 1005 4

 

TEST EXAMPLE 4: TEST OF SELECTIVITY FOR A CROP PLANT BY FLOODED PADDYFIELD TREATMENT

In a 100 cm² plastic pot, a paddy field soil was filled and paddled.Then, seeds of barnyard grass (Eo) and monochoria (Mo) were sown, andrice (Or) of second leaf stage was transplanted, and water wasintroduced to a depth of 3 cm. Next day, a wettable powder prepared inaccordance with Formulation Example 1 was diluted with water anddropwise applied to the water surface. The dose was 25 g of the activeingredient per 10 ares. Thereafter, cultivation was carried out in agreen house, and on the 21st day after the treatment, the herbicidaleffects were examined in accordance with the standards of Table 44. Theresults are shown in Tables 65 to 69.

TABLE 65 Compound No. Dose (gai/10s) Eo Mo Or 1-4 25 5 4 1 1-13 25 5 5 11-16 25 5 5 1 1-17 25 5 5 1 1-18 25 5 4 1 1-20 25 5 5 1 1-21 25 5 5 11-22 25 5 5 1 1-23 25 5 5 1 1-26 25 5 5 1 1-33 25 5 5 1 1-34 25 5 5 11-36 25 5 5 1 1-38 25 5 5 0 1-39 25 5 5 0 1-40 25 5 5 0 1-41 25 5 5 01-42 25 5 5 0 1-43 25 5 5 1 1-44 25 5 5 0 1-45 25 5 5 0 1-46 25 5 5 01-47 25 5 5 0 1-48 25 5 5 1 1-49 25 5 5 0 1-50 25 5 5 1 1-51 25 5 5 11-52 25 5 5 1 1-53 25 5 5 1 1-54 25 5 5 1 1-55 25 5 5 1 1-59 25 5 5 01-60 25 5 5 1 1-61 25 5 5 1 1-62 25 5 5 1 1-63 25 5 5 1 1-67 25 5 5 11-72 25 5 5 0 1-74 25 5 5 0 1-76 25 5 5 0 1-78 25 5 5 1 1-81 25 5 5 01-82 25 5 5 0 1-83 25 5 5 1 1-84 25 5 5 0 1-85 25 5 5 0 1-86 25 5 5 01-87 25 5 5 1 1-89 25 5 5 0 1-91 25 5 5 1 1-93 25 5 5 0 1-97 25 5 5 01-98 25 5 5 1

 

TABLE 66 Compound No. Dose (gai/10a) Eo Mo Or 1-99 25 5 5 1 1-103 25 5 51 1-104 25 5 5 1 1-106 25 5 5 0 1-107 25 5 5 0 1-113 25 5 5 0 1-116 25 55 0 1-118 25 5 3 0 1-119 25 5 5 0 1-120 25 5 5 0 1-121 25 5 5 1 1-123 255 5 1 1-124 25 5 5 0 1-125 25 5 5 0 1-126 25 5 5 1 1-130 25 5 5 1 1-13125 5 5 1 1-132 25 5 5 0 1-133 25 5 5 1 1-134 25 5 5 0 1-135 25 5 5 11-136 25 5 5 1 1-137 25 5 5 1 1-139 25 5 5 0 1-140 25 5 5 0 1-141 25 5 51 1-144 25 5 5 1 1-145 25 5 5 1 1-146 25 5 5 1 1-147 25 5 5 1 1-150 25 55 1 1-152 25 5 5 1 1-153 25 5 5 1 1-161 25 5 5 0 1-162 25 5 5 0 1-166 255 5 1 1-167 25 5 5 1 1-168 25 5 5 1 1-169 25 5 5 1 1-170 25 5 5 1 1-17125 5 5 1 1-172 25 5 5 1 1-175 25 5 5 0 1-180 25 5 5 1 1-181 25 5 5 11-182 25 5 5 1 1-183 25 5 5 0 1-188 25 5 5 0 1-189 25 5 5 0 1-190 25 5 50 1-197 25 5 5 0 1-200 25 5 5 1 1-217 25 5 5 1

 

TABLE 67 Compound No. Dose (gai/10a) Eo Mo Or 1-218 25 5 5 1 1-219 25 55 1 1-220 25 5 5 1 1-221 25 5 5 1 1-225 25 5 5 0 1-226 25 5 5 1 1-228 255 5 0 1-234 25 5 5 1 1-250 25 5 5 1 1-251 25 5 5 1 1-306 25 5 5 1 1-32125 5 5 1 1-324 25 5 5 1 1-325 25 5 5 1 1-329 25 5 5 1 1-333 25 5 5 11-334 25 5 5 0 1-401 25 5 5 1 1-404 25 5 5 1 1-412 25 5 5 1 1-416 25 5 51 1-417 25 5 5 1 1-418 25 5 5 1 1-425 25 5 5 1 1-436 25 5 5 1 1-439 25 55 1 1-441 25 5 5 1 1-442 25 5 5 1 1-443 25 5 5 1 1-444 25 5 5 1 1-448 255 5 1 1-452 25 5 5 0 1-454 25 5 5 1 1-455 25 5 5 1 1-459 25 5 5 1 1-46125 5 5 1 1-465 25 5 5 0 1-473 25 5 5 1 1-483 25 5 5 1 1-484 25 5 5 11-485 25 5 5 1 1-486 25 5 5 1 1-487 25 5 5 1 1-489 25 5 5 1 1-490 25 5 50 1-491 25 5 5 0 1-492 25 5 5 0 1-493 25 5 5 1 1-494 25 5 5 1 1-495 25 55 0 1-496 25 5 5 1 1-498 25 5 5 0 1-504 25 5 5 1

 

TABLE 68 Compound No. Dose (gai/10a) Eo Mo Or 1-505 25 5 5 0 1-506 25 55 1 1-507 25 5 5 1 1-511 25 5 5 0 1-517 25 5 5 1 1-519 26 5 5 1 1-520 255 5 1 1-521 25 5 5 1 1-527 25 5 5 1 1-528 25 5 5 1 1-529 25 5 5 1 1-53025 5 5 1 1-532 25 5 5 1 1-533 25 5 5 1 1-541 25 5 5 1 1-547 25 5 5 11-548 25 5 5 1 1-549 25 5 5 0 1-551 25 5 5 0 1-553 25 5 5 1 1-558 25 5 51 1-566 25 5 5 1 1-567 25 5 5 1 1-569 25 5 5 1 1-572 25 5 5 1 1-573 25 55 1 1-579 25 5 5 1 1-584 25 5 5 1 1-559 25 5 5 1 1-591 25 5 5 1 1-593 255 4 0 1-594 25 5 5 1 1-598 25 5 5 1 1-599 25 5 5 1 1-604 25 5 5 1 1-60625 5 5 1 1-607 25 5 5 1 1-608 25 5 5 1 1-609 25 5 5 1 1-611 25 5 5 11-614 25 5 5 1 1-615 25 5 5 1 1-624 25 5 5 1 1-626 25 5 5 1 1-627 25 5 51 1-639 25 5 4 1 2-1 25 5 5 0 2-2 25 5 5 1 2-7 25 5 5 1 2-8 25 5 5 02-19 25 5 5 1 2-20 25 5 5 1 2-25 25 5 5 1

 

TABLE 69 Compound No. Dose (gai/10a) Eo Mo Or 2-31 25 5 5 0 2-32 25 5 51 2-42 25 5 5 0 2-48 25 5 5 1 2-50 25 5 5 1 2-55 25 5 5 1 2-56 25 5 5 12-57 25 5 5 1 2-58 25 5 5 1 2-71 25 5 5 1 2-73 25 5 5 1 2-74 25 5 5 12-75 25 5 5 1 2-78 25 5 5 1 4-1 25 5 5 1 4-2 25 5 5 1

 

TEST EXAMPLE 5: TEST OF SELECTIVITY FOR A CROP PLANT BY SOIL TREATMENTIN UPLAND FIELD

In a 80 cm² plastic pot, upland soil was filled, and seeds of barnyardgrass (Ec), green foxtail (Se), soybean (G1), wheat (Tr) and corn (Ze)were sown and covered with soil. A wettable powder prepared inaccordance with Formulation Example 1 was diluted with water anduniformly applied to the soil surface by a small size spray at a rate of100 l per 10 ares so that the dose of the active ingredient would be 25g per 10 ares. Thereafter, cultivation was carried out in a green house,and on the 21st day after the treatment, the herbicidal effects wereexamined in accordance with the standards of Table 44. The results areshown in Table 70.

TABLE 70 Compound No. Dose (gai/10a) Ec Se Gl Tr Ze 1-15 25 5 5 — 1 11-23 25 5 5 — 2 1 1-33 25 4 4 0 2 1 1-42 25 5 5 0 0 0 1-45 25 4 5 0 2 01-46 25 5 5 1 3 0 1-48 25 4 5 0 1 0 1-49 25 5 5 1 0 3 1-50 25 4 5 3 3 01-51 25 5 5 0 1 0 1-53 25 4 5 1 2 0 1-54 25 4 5 0 1 0 1-55 25 5 4 1 1 01-56 25 5 5 0 4 3 1-58 25 5 5 0 3 0 1-59 25 5 5 0 1 0 1-60 25 5 5 1 2 01-61 25 5 5 1 3 0 1-64 25 4 4 2 3 0 1-65 25 5 5 0 0 0 1-68 25 4 4 0 2 21-70 25 5 4 1 4 1 1-71 25 5 5 — 3 0 1-75 25 4 4 0 3 2 1-76 25 4 4 0 2 21-77 25 5 5 1 3 2 1-78 25 5 5 0 1 0 1-80 25 5 5 0 5 1 1-81 25 4 4 0 1 01-83 25 5 5 1 2 1 1-84 25 4 4 0 1 0 1-85 25 4 4 0 1 0 1-89 25 4 5 0 2 21-95 25 5 5 1 0 0 1-97 25 4 4 3 1 0 1-98 25 4 5 0 1 1 1-99 25 4 4 0 3 01-100 25 5 5 0 2 2

 

Industrial Applicability

The compound of the present invention represented by the formula [I]exhibits excellent herbicidal effects over a wide range frompreemergence to the growing period of various weeds which areproblematic in upland fields, including, for example, broad leaf weedssuch as smartweed, slender amaranth, lambsquaters, chickweed,velvetleaf, prickly sida, hemp sesbania, morning glory and cocklebur,perenial and annual cyperaceous weeds such as purple nutsedge, yellownutsedge, himekugu, chufa and rice flatsedge, and glass weeds such asbarnyard grass, crab grass, green foxtail, annual bluegrass, Johnsongrass, water foxtail and wild oat. Further, it can control annual weedssuch as barnyard grass, umbrella plant and monochoria, and perenialweeds such as Japanese ribbon wapato, arrowhead, water nutgrass, waterchestnut, Japanese bulrush and narrowleaf waterplantain, which germinatein paddy fields. On the other hand, the herbicide of the presentinvetion has high safety to crop plants and exhibits particularly highsafety to rice, wheat, barley, corn, grain solgum, soybean, cotton,beet, etc.

What is claimed is:
 1. A pyrimidine derivative represented by theformula (I)

wherein R¹ is a hydrogen atom (except for a case where R² hydrogen atom,and W═SO₂), a halogen atom, a C₁-C₆ alkyl group, a C₁-C₆ alkylcarbonylC₁-C₆ alkyl group, a hydroxyl group, a C₂-C₆ alkenyl group, a C₂-C₆alkynyl group, a C₃-C₆ cycloalkyl group (this group may be substitutedby a halogen atom, a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group or a C₁-C₄haloalkyl group), a C₁-C₄ haloalkyl group, a C₁-C₆ alkoxy group, a C₁-C₄haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₂-C₆ alkynyloxy group, aC₃-C₆ cycloalkyloxy group, a phenyl group (this group may be substitutedby a halogen atom, a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group, a C₁-C₄haloalkyl group, a C₁-C₄ haloalkoxy group, a cyano group, a cyano C₁-C₆alkyl group, a nitro group, a C₁-C₆ alkylthio group, a C₁-C₆alkylsulfinyl group or a C₁-C₆ alkylsulfonyl group), a C₁-C₆ alkylthiogroup (except for a case where R²=phenyl group, and W═SO₂), a C₂-C₆alkenylthio group, a C₂-C₆ alkynylthio group, a C₃-C₆ cycloalkylthiogroup, a C₁-C₆ alkylsulfinyl group, a C₂-C₆ alkenylsulfinyl group, aC₂-C₆ alkynylsulfinyl group, a C₃-C₆ cycloalkylsulfinyl group, a C₁-C₆alkylsulfonyl group, a C₂-C₆ alkenylsulfonyl group, a C₂-C₆alkynylsulfonyl group, a C₃-C₆ cycloalkylsulfonyl group, a C₁-C₆hydroxyalkyl group, a C₂-C₇ acyl group, a C₁-C₆ alkoxy C₁-C₆ alkylgroup, a cyano group, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆alkoxycarbonyl C₁-C₆ alkyl group, a C₁-C₆ alkoxycarbonyl C₂-C₆ alkenylgroup, a carboxyl group, a carboxyl C₁-C₆ alkyl group, a di C₁-C₆ alkoxyC₁-C₆ alkyl group, a C₁-C₆ alkoxyimino C₁-C₆ alkyl group, a hydroxyiminoC₁-C₆ alkyl group, a dioxolanyl group (this group may be substituted bya C₁-C₆ alkyl group), an aldehyde group, an oxiranyl group, a NR⁹R¹⁰group or a CONR⁹R¹⁰ group, and R⁹ is a hydrogen atom, a C₁-C₆ alkylgroup, a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₄ haloalkylgroup, a C₁-C₆ alkoxy C₁-C₆ alkyl group, a C₁-C₆ alkylthio C₁-C₆ alkylgroup, a C₃-C₆ cycloalkyl group, a C₂-C₇ acyl group or a C₁-C₆alkylsulfonyl group, and R¹⁰ is a C₁-C₆ alkyl group, a C₂-C₆ alkenylgroup, a C₂-C₆ alkynyl group, a C₁-C₄ haloalkyl group, a C₁-C₆ alkoxyC₁-C₆ alkyl group, a C₁-C₆ alkylthio C₁-C₆ alkyl group, a C₃-C₆cycloalkyl group, a C₂-C₇ acyl group, a C₁-C₆ alkylsulfonyl group, aC₁-C₆ alkoxycarbonyl group or a benzyloxycarbonyl group; R² is ahydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆alkynyl group, a C₁-C₆ alkylthio group, a C₁-C₄ haloalkyl group, a C₁-C₆alkoxy group, a C₁-C₆ alkoxy C₁-C₆ alkyl group, a C₁-C₆ alkylthio C₁-C₆alkyl group, a C₃-C₆ cycloalkyl group (this group may be substituted bya halogen atom, a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group or a C₁-C₄haloalkyl group), a C₂-C₇ acyl group, a cyano group, a di C₁-C₆ alkoxyC₁-C₆ alkyl group, a C₁-C₆ alkoxyimino C₁-C₆ alkyl group, a hydroxyiminoC₁-C₆ alkyl group, a a cyano C₁-C₆ alkyl group, a C₁-C₆ hydroxyalkylgroup, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆ alkoxycarbonyl C₁-C₆ alkylgroup, a CR¹¹R¹²NR⁹R¹⁰ group, a CONR⁹R¹⁰ group, a CR¹¹R¹²CONR⁹R¹⁰ groupor a group represented by the formulae R²-1 or R²-2:

and wherein X is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group, aC₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkoxy group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a NR⁹R¹⁰ group, a CONR⁹R¹⁰ group, aC₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₃-C₆ cycloalkyloxygroup, a C₂-C₇ acyl group, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆alkylthio group, a C₁-C₆ alkylsulfinyl group, a C₁-C₆ alkylsufonylgroup, a cyano group, a nitro group or a C₁-C₄ haloalkyl group, and n isan integer of from 1 to 3, and when n is an integer of 2 or 3, theplurality of X may be the same or different, and two adjacent loweralkoxy groups may be bonded to each other to form a C₁-C₃ alkylenedioxygroup; each of R¹¹ and R¹² is a hydrogen atom, a C₁-C₆ alkyl group, aC₂-C₆ alkenyl group, a C₂-C₆ alkynyl group or a C₁-C₆ alkoxy group; R³is a hydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆alkynyl group, a C₁-C₆ alkoxy group, a di C₁-C₆ alkylamino group, aC₃-C₆ cycloalkyl group, a C₁-C₆ alkoxy C₁-C₆ alkyl group, a cyano C₁-C₆alkyl group, a C₃-C₆ cycloalkyl C₁-C₆ alkyl group, an oxiranyl C₁-C₆alkyl group or a C₁-C₆ alkoxycarbonyl C₁-C₆ alkyl group; W is a —C(═Q)Z—group or a —SO₂— group, Q is an oxygen atom or a sulfur atom, Z is anoxygen atom, a sulfur atom, a —NR⁶— group, a —CH₂CH₂— group, a —CH═CH—group, a —C(R⁴)R⁵— group, a —C(R⁴)R⁵—Q— group, a —Q—C(R⁴)R⁵— group, a—C(═Q)— group, a —NR⁶NR^(6a)— group or a —NR⁶C(R⁴)R⁵— group, and each ofR⁴ and R⁵ is a hydrogen atom, a C₁-C₆ alkyl group, a halogen atom, aC₁-C₆ alkoxy group or a C₁-C₆ alkylthio group, each of R⁶ and R^(6a) isa hydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group or a C₂-C₆alkynyl group; Ar is a group represented by the formulae Ar-1 or Ar-2:

  and wherein X′ is a hydrogen atom, a halogen atom, a C₁-C₆ alkylgroup, a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkoxygroup, a C₁-C₆ alkoxy C₁-C₆ alkyl group, a NR⁹R¹⁰ group, a CONR⁹R¹⁰group, a C₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₃-C₆cycloalkyloxy group, a C₂-C₇ acyl group, a C₁-C₆ alkoxycarbonyl group, aC₁-C₆ alkylthio group, a C₁-C₆ alkylsulfinyl group, a C₁-C₆ alkylsufonylgroup, a cyano group, a nitro group or a C₁-C₄ haloalkyl group, n′ is aninteger of from 1 to 3, and when n′ is an integer of 2 or 3, theplurality of X′ may be the same or different, and two adjacent loweralkoxy groups may be bonded to each other to form a C₁-C₃ alkylenedioxygroup; R⁷ is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group, aC₁-C₆ alkoxy group, a C₁-C₆ alkylthio group, (except for a case where R¹is a hydrogen atom and R² is a phenyl group and W is SO₂), a C₁-C₄haloalkyl group or a C₃-C₆ cycloalkyl group; and R⁸ is a hydrogen atom,a C₁-C₆ alkyl group, a C₁-C₆ alkylthio group, a C₁-C₄ haloalkyl group ora C₃-C₆ cycloalkyl group.
 2. A pyrimidine derivative represented by theformula

wherein R¹ is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group, aC₁-C₆ alkylcarbonyl C₁-C₆ alkyl group, a hydroxyl group, a C₂-C₆ alkenylgroup, a C₂-C₆ alkynyl group, a C₃-C₆ cycloalkyl group (this group maybe substituted by a halogen atom, a C₁-C₆ alkyl group, a C₁-C₆ alkoxygroup or a C₁-C₄ haloalkyl group), a C₁-C₄ haloalkyl group, a C₁-C₆alkoxy group, a C₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, aC₂-C₆ alkynyloxy group, a C₃-C₆ cycloalkyloxy group, a phenyl group(this group may be substituted by a halogen atom, a C₁-C₆ alkyl group, aC₁-C₆ alkoxy group, a C₁-C₄ haloalkyl group, a C₁-C₄ haloalkoxy group, acyano group, a nitro group, a C₁-C₆ alkylthio group, a C₁-C₆alkylsulfinyl group or a C₁-C₆ alkylsulfonyl group), a C₁-C₆ alkylthiogroup, a C₂-C₆ alkenylthio group, a C₂-C₆ atkynylthio group, a C₃-C₆cycloalkylthio group, a C₁-C₆ alkylsulfinyl group, a C₂-C₆alkenylsulfinyl group, a C₂-C₆ alkynylsulfinyl group, a C₃-C₆cycloalkylsulfinyl group, a C₁-C₆ alkylsulfonyl group, a C₂-C₆alkenylsulfonyl group, a C₂-C₆ alkynylsulfonyl group, a C₃-C₆cycloalkylsulfonyl group, a hydroxyalkyl group, a C₂-C₇ acyl group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a cyano group, a cyano C₁-C₆ alkylgroup, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆ alkoxycarbonyl C₁-C₆ alkylgroup, a C₁-C₆ alkoxycarbonyl C₂-C₆ alkenyl group, a carboxyl group, acarboxyl C₁-C₆ alkyl group, a di C₁-C₆ alkoxy C₁-C₆ alkyl group, a C₁-C₆alkoxyimino C₁-C₆ alkyl group, a hydroxyimino C₁-C₆ alkyl group, adioxolanyl group (this group may be substituted by a C₁-C₆ alkyl group),an aldehyde group, an oxiranyl group, a NR⁹R¹⁰ group or a CONR⁹R¹⁰group, and R⁹ is a hydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆ alkenylgroup, a C₂-C₆ alkynyl group, a C₁-C₄ haloalkyl group, a C₁-C₆ alkoxyC₁-C₆ alkyl group, a C₁-C₆ alkylthio C₁-C₆ alkyl group, a C₃-C₆cycloalkyl group, a C₂-C₇ acyl group or a C₁-C₆ alkylsulfonyl group, andR¹⁰ is a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆ alkynylgroup, a C₁-C₄ haloalkyl group, a C₁-C₆ alkoxy C₁-C₆ alkyl group, aC₁-C₆ alkylthio C₁-C₆ alkyl group, a C₃-C₆ cycloalkyl group, a C₂-C₇acyl group, a C₁-C₆ alkylsulfonyl group, a C₁-C₆ alkoxycarbonyl group ora benzyloxycarbonyl group; R² is a hydrogen atom, a C₁-C₆ alkyl group, aC₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkylthio group, aC₁-C₄ haloalkyl group, a C₁-C₆ alkoxy group, a C₁-C₆ alkoxy C₁-C₆ alkylgroup, a C₁-C₆ alkylthio C₁-C₆ alkyl group, a C₃-C₆ cycloalkyl group(this group may be substituted by a halogen atom, a C₁-C₆ alkyl group, aC₁-C₆ alkoxy group or a C₁-C₄ haloalkyl group), a C₂-C₇ acyl group, acyano group, a di C₁-C₆ alkoxy C₁-C₆ alkyl group, a C₁-C₆ alkoxyiminoC₁-C₆ alkyl group, a hydroxyimino C₁-C₆ alkyl group, a a cyano C₁-C₆alkyl group, a C₁-C₆ hydroxyalkyl group, a C₁-C₆ alkoxycarbonyl group, aC₁-C₆ alkoxycarbonyl C₁-C₆ alkyl group, a CR¹¹R¹²NR⁹R¹⁰ group, aCONR⁹R¹⁰ group, a CR¹¹R¹²CONR⁹R¹⁰ group or a group represented by theformulae R²-1 or R²-2:

and wherein X is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group, aC₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkoxy group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a NR⁹R¹⁰ group, a CONR⁹R¹⁰ group, aC₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₃-C₆ cycloalkyloxygroup, a C₂-C₇ acyl group, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆alkylthio group, a C₁-C₆ alkylsulfinyl group, a C₁-C₆ alkylsufonylgroup, a cyano group, a nitro group or a C₁-C₄ haloalkyl group, n is aninteger of from 1 to 3, and when n is an integer of 2 or 3, theplurality of X may be the same or different, and two adjacent loweralkoxy groups may be bonded to each other to form a C₁-C₃ alkylenedioxygroup, and each of R¹¹ and R¹² is a hydrogen atom, a C₁-C₆ alkyl group,a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group or a C₁-C₆ alkoxy group; R³is a hydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆alkynyl group, a C₁-C₆ alkoxy group, a di C₁-C₆ alkylamino group, aC₃-C₆ cycloalkyl group, a C₁-C₆ alkoxy C₁-C₆ alkyl group, a cyano C₁-C₆alkyl group, a C₃-C₆ cycloalkyl C₁-C₆ alkyl group, an oxiranyl C₁-C₆alkyl group or a C₁-C₆ alkoxycarbonyl C₁-C₆ alkyl group; W is a —C(═Q)Z—group, Q is an oxygen atom or a sulfur atom, Z is an oxygen atom, asulfur atom, a —NR⁶— group, a —CH₂CH₂— group, a —CH═CH— group, a—C(R⁴)R⁵— group, a —C(R⁴)R⁵—Q— group, a —Q—C(R⁴)R⁵— group, a —C(═Q)—group, a —NR⁶NR^(6a) group or a —NR⁶C(R⁴)R⁵— group, each of R⁴ and R⁵ isa hydrogen atom, a C₁-C₆ alkyl group, a halogen atom, a C₁-C₆ alkoxygroup or a C₁-C₆ alkylthio group, each of R⁶ and R^(6a) is a hydrogenatom, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group or a C₂-C₆ alkynylgroup; Ar is a group represented by the formulae Ar to Ar-1 or Ar-2:

  and wherein X′ is a hydrogen atom, a halogen atom, a C₁-C₆ alkylgroup, a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkoxygroup, a C₁-C₆ alkoxy C₁-C₆ alkyl group, a NR⁹R¹⁰ group, a CONR⁹R¹⁰group, a C₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₃-C₆cycloalkyloxy group, a C₂-C₇ acyl group, a C₁-C₆ alkoxycarbonyl group, aC₁-C₆ alkylthio group, a C₁-C₆ alkylsulfinyl group, a C₁-C₆ alkylsufonylgroup, a cyano group, a nitro group or a C₁-C₄ haloalkyl group, n′ is aninteger of from 1 to 3, and when n′ is an integer of 2 or 3, theplurality of X′ may be the same or different, and two adjacent loweralkoxy groups may be bonded to each other to form a C₁-C₃ alkylenedioxygroup); R⁷ is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group, aC₁-C₆ alkoxy group, a C₁-C₆ alkylthio group, a C₁-C₄ haloalkyl group ora C₃-C₆ cycloalkyl group; and R⁸ is a hydrogen atom, a C₁-C₆ alkylgroup, a C₁-C₆ alkylthio group, a C₁-C₄ haloalkyl group or a C₃-C₆cycloalkyl group.
 3. A pyrimidine derivative represented by the formula

wherein R¹ is a halogen atom, a C₁-C₆ alkyl group, an oxo C₁-C₆ alkylgroup, a hydroxyl group, a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, aC₃-C₆ cycloalkyl group (this group may be substituted by a halogen atom,a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group or a C₁-C₄ haloalkyl group), aC₁-C₄ haloalkyl group, a C₁-C₆ alkoxy group, a C₁-C₄ haloalkoxy group, aC₂-C₆ alkenyloxy group, a C₂-C₆ alkynyloxy group, a C₃-C₆ cycloalkyloxygroup, a phenyl group (this group may be substituted by a halogen atom,a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group, a C₁-C₄ haloalkyl group, aC₁-C₄ haloalkoxy group, a cyano group, a nitro group, a C₁-C₆ alkylthiogroup, a C₁-C₆ alkylsulfinyl group or a C₁-C₆ alkylsulfonyl group), aC₂-C₆ alkenylthio group, a C₂-C₆ alkynylthio group, a C₃-C₆cycloalkylthio group, a C₁-C₆ alkylsulfinyl group, a C₂-C₆alkenylsulfinyl group, a C₂-C₆ alkynylsulfinyl group, a C₃-C₆cycloalkylsulfinyl group, a C₁-C₆ alkylsulfonyl group, a C₂-C₆alkenylsulfonyl group, a C₂-C₆ alkynylsulfonyl group, a C₃-C₆cycloalkylsulfonyl group, a hydroxyalkyl group, a C₂-C₇ acyl group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a cyano group, a cyano C₁-C₆ alkylgroup, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆ alkoxycarbonyl C₁-C₆ alkylgroup, a C₁-C₆ alkoxycarbonyl C₂-C₆ alkenyl group, a carboxyl group, acarboxyl C₁-C₆ alkyl group, a di C₁-C₆ alkoxy C₁-C₆ alkyl group, a C₁-C₆alkoxyimino C₁-C₆ alkyl group, a hydroxyimino C₁-C₆ alkyl group, adioxolanyl group (this group may be substituted by a C₁-C₆ alkyl group),an aldehyde group, an oxiranyl group, a NR⁹R¹⁰ group or a CONR⁹R¹⁰group, and R⁹ is a hydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆ alkenylgroup, a C₂-C₆ alkynyl group, a C₁-C₄ haloalkyl group, a C₁-C₆ alkoxyC₁-C₆ alkyl group, a C₁-C₆ alkylthio C₁-C₆ alkyl group, a C₃-C₆cycloalkyl group, a C₂-C₇ acyl group or a C₁-C₆ alkylsulfonyl group, andR¹⁰ is a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆ alkynylgroup, a C₁-C₄ haloalkyl group, a C₁-C₆ alkoxy C₁-C₆ alkyl group, aC₁-C₆ alkylthio C₁-C₆ alkyl group, a C₃-C₆ cycloalkyl group, a C₂-C₇acyl group, a C₁-C₆ alkylsulfonyl group, a C₁-C₆ alkoxycarbonyl group ora benzyloxycarbonyl group; R² is a hydrogen atom, a C₁-C₆ alkyl group, aC₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkylthio group, aC₁-C₄ haloalkyl group, a C₁-C₆ alkoxy group, a C₁-C₆ alkoxy C₁-C₆ alkylgroup, a C₁-C₆ alkylthio C₁-C₆ alkyl group, a C₃-C₆ cycloalkyl group(this group may be substituted by a halogen atom, a C₁-C₆ alkyl group, aC₁-C₆ alkoxy group or a C₁-C₄ haloalkyl group), a C₂-C₇ acyl group, acyano group, a di C₁-C₆ alkoxy C₁-C₆ alkyl group, a C₁-C₆ alkoxyiminoC₁-C₆ alkyl group, a hydroxyimino C₁-C₆ alkyl group, a a cyano C₁-C₆alkyl group, a C₁-C₆ hydroxyalkyl group, a C₁-C₆ alkoxycarbonyl group, aC₁-C₆ alkoxycarbonyl C₁-C₆ alkyl group, a CR¹¹R¹²NR⁹R¹⁰ group, aCONR⁹R¹⁰ group, a CR¹¹R¹²CONR⁹R¹⁰ group or a group represented by theformulae R²-1 or R²-2:

and (wherein X is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group,a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkoxy group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a NR⁹R¹⁰ group, a CONR⁹R¹⁰ group, aC₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₃-C₆ cycloalkyloxygroup, a C₂-C₇ acyl group, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆alkylthio group, a C₁-C₆ alkylsulfinyl group, a C₁-C₆ alkylsufonylgroup, a cyano group, a nitro group or a C₁-C₄ haloalkyl group, n is aninteger of from 1 to 3, and when n is an integer of 2 or 3, theplurality of X may be the same or different, and two adjacent loweralkoxy groups may be bonded to each other to form a C₁-C₃ alkylenedioxygroup), and each of R¹¹ and R¹² is a hydrogen atom, a C₁-C₆ alkyl group,a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group or a C₁-C₆ alkoxy group; R³is a hydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆alkynyl group, a C₁-C₆ alkoxy group, a di C₁-C₆ alkylamino group, aC₃-C₆ cycloalkyl group, a C₁-C₆ alkoxy C₁-C₆ alkyl group, a cyano C₁-C₆alkyl group, a C₃-C₆ cycloalkyl C₁-C₆ alkyl group, an oxiranyl C₁-C₆alkyl group or a C₁-C₆ alkoxycarbonyl C₁-C₆ alkyl group; W is a —SO₂—group; Ar is a group represented by the formulae Ar-1 or Ar-2:

  and wherein X′ is a hydrogen atom, a halogen atom, an alkyl group, aC₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkoxy group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a NR⁹R¹⁰ group, a CONR⁹R¹⁰ group, aC₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₃-C₆ cycloalkyloxygroup, a C₂-C₇ acyl group, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆alkylthio group, a C₁-C₆ alkylsulfinyl group, a C₁-C₆ alkylsufonylgroup, a cyano group, a nitro group or a C₁-C₄ haloalkyl group, n′ is aninteger of from 1 to 3, and when n′ is an integer of 2 or 3, theplurality of X′ may be the same or different, and two adjacent loweralkoxy groups may be bonded to each other to form a C₁-C₃ alkylenedioxygroup; R⁷ is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group, aC₁-C₆ alkoxy group, a C₁-C₆ alkylthio group, a C₁-C₄ haloalkyl group ora C₃-C₆ cycloalkyl group; and R⁸ is a hydrogen atom, a C₁-C₆ alkylgroup, a C₁-C₆ alkylthio group, a C₁-C₄ haloalkyl group or a C₃-C₆cycloalkyl group.
 4. A pyrimidine derivative represented by the formula

  wherein R¹ is a halogen atom, a C₁-C₆ alkyl group, a C₁-C₆alkylcarbonyl C₁-C₆ alkyl group, a hydroxyl group, a C₂-C₆ alkenylgroup, a C₂-C₆ alkynyl group, a C₃-C₆ cycloalkyl group (this group maybe substituted by a halogen atom, a C₁-C₆ alkyl group, a C₁-C₆ alkoxygroup or a C₁-C₄ haloalkyl group), a C₁-C₄ haloalkyl group, a C₁-C₆alkoxy group, a C₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, aC₂-C₆ alkynyloxy group, a C₃-C₆ cycloalkyloxy group, a phenyl group(this group may be substituted by a halogen atom, a C₁-C₆ alkyl group, aC₁-C₆ alkoxy group, a C₁-C₄ haloalkyl group, a C₁-C₄ haloalkoxy group, acyano group, a nitro group, a C₁-C₆ alkylthio group, a C₁-C₆alkylsulfinyl group or a C₁-C₆ alkylsulfonyl group), a C₁-C₆ alkylthiogroup (except for a case where R² =phenyl group, and W═SO₂), a C₂-C₆alkenylthio group, a C₂-C₆ alkynylthio group, a C₃-C₆ cycloalkylthiogroup, a C₁-C₆ alkylsulfinyl group, a C₂-C₆ alkenylsulfinyl group, aC₂-C₆ alkynylsulfinyl group, a C₃-C₆ cycloalkylsulfinyl group, a C₁-C₆alkylsulfonyl group, a C₂-C₆ alkenylsulfonyl group, a C₂-C₆alkynylsulfonyl group, a C₃-C₆ cycloalkylsulfonyl group, a C₁-C₆hydroxyalkyl group, a C₂-C₇ acyl group, a C₁-C₆ alkoxy C₁-C₆ alkylgroup, a cyano group, a cyano C₁-C₆ alkyl group, a C₁-C₆ alkoxycarbonylgroup, a C₁-C₆ alkoxycarbonyl C₁-C₆ alkyl group, a C₁-C₆ alkoxycarbonylC₂-C₆ alkenyl group, a carboxyl group, a carboxyl C₁-C₆ alkyl group, adi C₁-C₆ alkoxy C₁-C₆ alkyl group, a C₁-C₆ alkoxyimino C₁-C₆ alkylgroup, a hydroxyimino C₁-C₆ alkyl group, a dioxolanyl group (this groupmay be substituted by a C₁-C₆ alkyl group), an aldehyde group, anoxiranyl group, a NR⁹R¹⁰ group or a CONR⁹R¹⁰ group, and R⁹ is a hydrogenatom, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group,a C₁-C₄ haloalkyl group, a C₁-C₆ alkoxy C₁-C₆ alkyl group, a C₁-C₆alkylthio C₁-C₆ alkyl group, a C₃-C₆ cycloalkyl group, a C₂-C₇ acylgroup or a C₁-C₆ alkylsulfonyl group, and R¹⁰ is a C₁-C₆ alkyl group, aC₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₄ haloalkyl group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a C₁-C₆ alkylthio C₁-C₆ alkyl group, aC₃-C₆ cycloalkyl group, a C₂-C₇ acyl group, a C₁-C₆ alkylsulfonyl group,a C₁-C₆ alkoxycarbonyl group or a benzyloxycarbonyl group; R² is a C₁-C₆alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆alkylthio group, a C₁-C₄ haloalkyl group, a C₁-C₆ alkoxy group, a C₁-C₆alkoxy C₁-C₆ alkyl group, a C₁-C₆ alkylthio C₁-C₆ alkyl group, a C₃-C₆cycloalkyl group (this group may be substituted by a halogen atom, aC₁-C₆ alkyl group, a C₁-C₆ alkoxy group or a C₁-C₄ haloalkyl group), aC₂-C₇ acyl group, a cyano group, a di C₁-C₆ alkoxy C₁-C₆ alkyl group, aC₁-C₆ alkoxyimino C₁-C₆ alkyl group, a hydroxyimino C₁-C₆ alkyl group, aa cyano C₁-C₆ alkyl group, a C₁-C₆ hydroxyalkyl group, a C₁-C₆alkoxycarbonyl group, a C₁-C₆ alkoxycarbonyl C₁-C₆ alkyl group, aCR¹¹R¹²NR⁹R¹⁰ group, a CONR⁹R¹⁰ group, a CR¹¹R¹²CONR⁹R¹⁰ group or agroup represented by the formulae R²-1 or R²-2:

  and wherein X is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group,a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkoxy group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a NR⁹R¹⁰ group, a CONR⁹R¹⁰ group, aC₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₃-C₆ cycloalkyloxygroup, a C₂-C₇ acyl group, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆alkylthio group, a C₁-C₆ alkylsulfinyl group, a C₁-C₆ alkylsufonylgroup, a cyano group, a nitro group or a C₁-C₄ haloalkyl group, n is aninteger of from 1 to 3, and when n is an integer of 2 or 3, theplurality of X may be the same or different, and two adjacent loweralkoxy groups may be bonded to each other to form a C₁-C₃ alkylenedioxygroup, and each of R¹¹ and R¹² is a hydrogen atom, a C₁-C₆ alkyl group,a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group or a C₁-C₆ alkoxy group; R³is a hydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆alkynyl group, a C₁-C₆ alkoxy group, a di C₁-C₆ alkylamino group, aC₃-C₆ cycloalkyl group, a C₁-C₆ alkoxy C₁-C₆ alkyl group, a cyano C₁-C₆alkyl group or a C₃-C₆ cycloalkyl C₁-C₆ alkyl group; W is a —C(═Q)Z—group or a —SO₂— group, Q is an oxygen atom or a sulfur atom, Z is anoxygen atom, a sulfur atom, a —NR⁶— group, a —C(R)R⁵— group, a—C(R⁴)R⁵—Q— group, a —NR⁶NR⁶— group or a —NR⁶C(R⁴)R⁵— group, and each ofR⁴ and R⁵ is a hydrogen atom, a C₁-C₆ alkyl group, a halogen atom or aC₁-C₆ alkoxy group, and each of R⁶ and R^(6a) is a hydrogen atom, aC₁-C₆ alkyl group, a C₂-C₆ alkenyl group or a C₂-C₆ alkynyl group; Ar isa group represented by any one of the formulae Ar-1 or Ar-2:

and wherein X′ is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group,a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkoxy group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a NR⁹R¹⁰ group, a CONR⁹R¹⁰ group, aC₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₃-C₆ cycloalkyloxygroup, a C₂-C₇ acyl group, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆alkylthio group, a C₁-C₆ alkylsulfinyl group, a C₁-C₆ alkylsufonylgroup, a cyano group, a nitro group or a C₁-C₄ haloalkyl group, n′ is aninteger of from 1 to 3, and when n′ is an integer of 2 or 3, theplurality of X′ may be the same or different, and two adjacent loweralkoxy groups may be bonded to each other to form a C₁-C₃ alkylenedioxygroup; R⁷ is a hydrogen atom or a halogen atom; and R⁸ is a hydrogenatom.
 5. A pyrimidine derivative represented by the formula

wherein R¹ is a C₁-C₆ alkyl group, a C₁-C₆ alkylcarbonyl C₁-C₆ alkylgroup, a C₃-C₆ cycloalkyl group (this group may be substituted by ahalogen atom, a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group or a C₁-C₄haloalkyl group), a C₁-C₄ haloalkyl group, a C₁-C₆ alkoxy group, aphenyl group (this group may be substituted by a halogen atom, a C₁-C₆alkyl group, a C₁-C₆ alkoxy group, a C₁-C₄ haloalkyl group, a C₁-C₄haloalkoxy group, a cyano group, a nitro group, a C₁-C₆ alkylthio group,a C₁-C₆ alkylsulfinyl group or a C₁-C₆ alkylsulfonyl group), a C₁-C₆alkylthio group (except for a case where R²=phenyl group, and W═SO₂), aC₁-C₆ alkylsulfinyl group, a C₂-C₇ acyl group, a C₁-C₆ alkoxy C₁-C₆alkyl group, a cyano group, a cyano C₁-C₆ alkyl group, a C₁-C₆alkoxycarbonyl group, a C₁-C₆ alkoxycarbonyl C₂-C₆ alkenyl group, acarboxyl group, a di C₁-C₆ alkoxy C₁-C₆ alkyl group or a C₁-C₆alkoxyimino C₁-C₆ alkyl group; R² is a C₁-C₆ alkyl group, a C₁-C₄haloalkyl group, a C₁-C₆ alkoxy C₁-C₆ alkyl group, a C₁-C₆ alkylthioC₁-C₆ alkyl group, a C₃-C₆ cycloalkyl group (this group may besubstituted by a halogen atom, a C₁-C₆ alkyl group, a C₁-C₆ alkoxy groupor a C₁-C₄ haloalkyl group) a C₂-C₇ acyl group, or a group representedby the formula R²-1:

and wherein X is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group, aC₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkoxy group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a NR⁹R¹⁰ group, a CONR⁹R¹⁰ group, aC₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₃-C₆ cycloalkyloxygroup, a C₂-C₇ acyl group, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆alkylthio group, a C₁-C₆ alkylsulfinyl group, a C₁-C₆ alkylsufonylgroup, a cyano group, a nitro group or a C₁-C₄ haloalkyl group, n is aninteger of from 1 to 3, and when n is an integer of 2 or 3, theplurality of X may be the same or different, and two adjacent loweralkoxy groups may be bonded to each other to form a C₁-C₃ alkylenedioxygroup, and R⁹ is a hydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆ alkenylgroup, a C₂-C₆ alkynyl group, a C₁-C₄ haloalkyl group, a C₁-C₆ alkoxyC₁-C₆ alkyl group, a C₁-C₆ alkylthio C₁-C₆ alkyl group, a C₃-C₆cycloalkyl group, a C₂-C₇ acyl group or a C₁-C₆ alkylsulfonyl group, andR¹⁰ is a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆ alkynylgroup, a C₁-C₄ haloalkyl group, a C₁-C₆ alkoxy C₁-C₆ alkyl group, aC₁-C₆ alkylthio C₁-C₆ alkyl group, a C₃-C₆ cycloalkyl group, a C₂-C₇acyl group, a C₁-C₆ alkylsulfonyl group, a C₁-C₆ alkoxycarbonyl group ora benzyloxycarbonyl group, and each of R¹¹ and R¹² is a hydrogen atom, aC₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group or aC₁-C₆ alkoxy group; R³ is a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, aC₂-C₆ alkynyl group, a C₁-C₆ alkoxy group, a C₃-C₆ cycloalkyl group, aC₁-C₆ alkoxy C₁-C₆ alkyl group or a cyano C₁-C₆ alkyl group; W is a—C(═Q)Z— group or a —SO₂— group, Q is an oxygen atom or a sulfur atom, Zis a —NR⁶— group, a —C(R⁴)R⁵— group, a —C(R⁴)R⁵—Q— group, a —NRR^(6a)—group or a —NR⁶C(R⁴)R⁵— group, and each of R⁴ and R⁵ is a hydrogen atom,a C₁-C₆ alkyl group, a halogen atom or a C₁-C₆ alkoxy group, and each ofR⁶ and R^(6a) is a hydrogen atom, a C₁-C₆ alkyl group, a C₂-C₆ alkenylgroup or a C₂-C₆ alkynyl group; Ar is a group represented by formulaAr-1,

and wherein X′ is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group,a C₂-C₆ alkenyl group, a C₂-C₆ alkynyl group, a C₁-C₆ alkoxy group, aC₁-C₆ alkoxy C₁-C₆ alkyl group, a NR⁹R¹⁰ group, a CONR⁹R¹⁰ group, aC₁-C₄ haloalkoxy group, a C₂-C₆ alkenyloxy group, a C₃-C₆ cycloalkyloxygroup, a C₂-C₇ acyl group, a C₁-C₆ alkoxycarbonyl group, a C₁-C₆alkylthio group, a C₁-C₆ alkylsulfinyl group, a C₁-C₆ alkylsufonylgroup, a cyano group, a nitro group or a C₁-C₄ haloalkyl group, n′ is aninteger of from 1 to 3, and when n′ is an integer of 2 or 3, theplurality of X′ may be the same or different, and two adjacent loweralkoxy groups may be bonded to each other to form a C₁-C₃ alkylenedioxygroup; R⁷ is a hydrogen atom, a halogen atom, a C₁-C₆ alkyl group, aC₁-C₆ alkoxy group, a C₁-C₆ alkylthio group, a C₁-C₄ haloalkyl group ora C₃-C₆ cycloalkyl group, and R⁸ is a hydrogen atom, a C₁-C₆ alkylgroup, a C₁-C₆ alkylthio group, a C₁-C₄ haloalkyl group or a C₃-C₆cycloalkyl group.
 6. A herbicide containing the pyrimidine derivative asdefined in claim 1, as an active ingredient.
 7. A herbicide containingthe pyrimidine derivative as defined in claim 2, as an activeingredient.
 8. A herbicide containing the pyrimidine derivative asdefined in claim 3, as an active ingredient.
 9. A herbicide containingthe pyrimidine derivative as defined in claim 4, as an activeingredient.
 10. A herbicide containing the pyrimidine derivative asdefined in claim 5, as an active ingredient.